WO2006035908A1 - Silver paste composition - Google Patents

Silver paste composition Download PDF

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Publication number
WO2006035908A1
WO2006035908A1 PCT/JP2005/018030 JP2005018030W WO2006035908A1 WO 2006035908 A1 WO2006035908 A1 WO 2006035908A1 JP 2005018030 W JP2005018030 W JP 2005018030W WO 2006035908 A1 WO2006035908 A1 WO 2006035908A1
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WO
WIPO (PCT)
Prior art keywords
silver
paste composition
thin film
weight
organic
Prior art date
Application number
PCT/JP2005/018030
Other languages
French (fr)
Japanese (ja)
Inventor
Naosuke Ochiai
Original Assignee
Nippon Kin-Eki Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kin-Eki Co., Ltd. filed Critical Nippon Kin-Eki Co., Ltd.
Priority to JP2006537826A priority Critical patent/JPWO2006035908A1/en
Publication of WO2006035908A1 publication Critical patent/WO2006035908A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/136286—Wiring, e.g. gate line, drain line
    • G02F1/136295—Materials; Compositions; Manufacture processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder

Definitions

  • the present invention relates to a silver paste composition for forming a silver thin film used for a thin film conductor (resistor thin film electrode) of various electronic components and a wiring material of a display device.
  • the present invention also relates to a method for producing a silver thin film from the silver paste composition.
  • the present invention further provides a thin film conductor for electronic parts including the silver thin film and a wiring material for display.
  • the thinning of the terminal electrode is difficult to obtain with a so-called thick film electrode mixed with metal powder and an organic vehicle, and it is difficult to stably obtain a film thickness of 2.5 microns or less.
  • a photoresist pattern is formed, and the opening is removed by an etching method.
  • a method of obtaining a thin film mainly composed of gold by printing a paste with a thick film pattern and then baking the paste.
  • the formation of thin film electrodes by a vacuum technique requires expensive equipment such as a vacuum apparatus and an exposure apparatus, resulting in high equipment costs.
  • the thin-film electrode pattern formation method using gold metal organics is used in some high-end devices because the pattern formation process itself uses power gold, which is an inexpensive thick film technique, and its material cost is extremely high. Stays on.
  • the bus line conductor on the front panel of a PDP (plasma display panel) is an electrode thin film for improving the reliability of the dielectric formed on the bus line conductor. ⁇ is required.
  • reducing the thickness of the electrode leads to a significant cost reduction (reduction of precious metal consumption), so it has been realized even though it is extremely useful.
  • Patent Document 1 JP-A-6-45118
  • Patent Document 2 Japanese Patent Laid-Open No. 4-326791
  • An object of the present invention is to provide a dense and stable silver thin film having a small sheet resistance value of 2.5 microns or less, which is useful as a thin film conductor (resistor thin film electrode) for various electronic components and a wiring material for a display device. It is to provide a new silver paste composition to obtain.
  • a silver paste composition containing inorganic acid silver and Z or organic acid silver, an organic noder, and a solvent is inorganic from the viewpoint of paste viscosity.
  • the printing properties of this silver-based composition on the substrate are excellent, and 0.2% by heat drying and low-temperature sintering.
  • a stable and dense silver thin film can be formed within a thickness range of ⁇ 2.5 microns, and solved the above problems.
  • the inventors of the present invention have also found that the above-described silver thin film is useful for a thin film conductor (resistor thin film electrode) of various electronic components and a wiring material of a display device, thereby completing the present invention. .
  • the present invention provides the following.
  • a silver paste composition comprising:
  • a silver paste composition wherein the silver content based on component A) is from 10 to 50% by weight, based on the total weight of the composition.
  • Silver paste composition strength according to item (1) Obtained thin silver film having a thickness of 0.2 to 2.5 m (10) A thin film conductor for electronic parts, comprising the silver thin film according to item (9).
  • a display device wiring material comprising the silver thin film according to item (9).
  • a method for producing a silver thin film is a method for producing a silver thin film.
  • step a) is performed by screen printing.
  • step b) is performed at 90 to 150 ° C.
  • step c) is performed at 450 to 700 ° C.
  • a silver thin film having excellent conductivity can be patterned by a thick film technique such as screen printing, and a silver thin film of about 0.2 to 2.5 m can be formed on various substrates by firing. It is possible to obtain good adhesion.
  • the heat resistance of the film can be ensured by adding a sintering inhibitor as appropriate so that it can withstand baking at temperatures as low as 450 ° C or as high as 850 ° C.
  • a silver thin film electrode can be provided.
  • the “silver paste composition” means that silver is the most among the metal components contained in the composition, and a film is formed when applied on a “substrate” defined below. Can As long as it means a paste-like composition and satisfies the above requirements, the type and amount of each component constituting the composition are not particularly limited.
  • the term “silver paste composition” is used herein interchangeably with the term “silver paste”.
  • inorganic acid silver means a silver salt of an inorganic acid (an acid group formed by combining an acid group containing a nonmetal such as Cl, S, N, and P with hydrogen), Typical examples include silver carbonate and silver oxide.
  • the “organic acid silver” is a term for the above “inorganic acid silver”, and an organic acid containing one or more carboxyl groups (—COOH) in the molecule (for example, fatty acid, aromatic Acid or hydroxy acid).
  • fatty acid refers to an R—COOH having one carboxyl group (where R represents a hydrophobic chain) having a linear or branched, saturated or unsaturated chain structure.
  • R represents a hydrophobic chain
  • the carbon number of the fatty acid used in the present invention is not particularly limited, but C to C fatty acids generally used industrially are the present invention.
  • aromatic acid in the present invention is a general term for compounds in which one or more carboxyl groups are substituted on the aromatic ring. Typical examples include benzoic acid.
  • Hydrophilic acid in the present invention is a general term for organic compounds having —OH group and —COOH in the molecule, and typical examples include lactic acid.
  • the “organic binder” is used in the silver paste composition for the purpose of ensuring the stability and strength of a film formed by coating the silver paste composition of the present invention on a substrate.
  • solvent means that the components constituting the silver paste composition of the present invention are completely or at least partially dissolved, and the paste is added to the “silver paste composition” of the present invention. It refers to all organic solvents commonly used in the industry that give moderate viscosity as.
  • the “organic vehicle” means a solution in which an organic binder is dissolved in a solvent.
  • the term "silver content based on (component A))” refers to component A), that is, silver derived from inorganic acid silver and Z or organic acid silver as defined above. In this specification, Unless otherwise specified, it is not intended to be included in the silver paste composition of the present invention, and is not silver derived from other silver components (silver powder, silver particles, silver fine particles, silver pieces, etc.) or silver compounds, Means the silver content.
  • silver powder is not intended to be included in the silver paste composition of the present invention unless otherwise specified in the present specification, and is a conventional silver paste for forming a conductive thin film. It means a silver component having a relatively large particle diameter (for example, silver powder, silver particles, silver fine particles, silver pieces, etc., although the shape is not particularly limited).
  • substantially does not contain (silver powder) means that when a silver thin film is formed from the “silver paste composition” of the present invention, silver atoms are stabilized. It means that the silver paste composition of the present invention does not contain the above “silver powder” in an amount that inhibits the formation of a dense film or has an adverse effect.
  • the “silver thin film” means a stable and dense silver thin film having a thickness of 2.5 ⁇ m or less formed from the “silver paste composition” of the present invention by the method of the present invention. . Unless otherwise stated in this specification, it is distinguished from conventional silver thin films.
  • the "substrate” is anything that is compatible with the “silver paste composition” in terms of the applicability of the “silver paste composition” of the present invention applied thereon.
  • the material and shape of the “substrate” are not particularly limited.
  • the “film (of silver paste composition)” means a film formed by applying the “silver paste composition” of the present invention on a “substrate”.
  • drying the film means volatilizing at least a part of the solvent from the “film (of the silver paste composition)” defined above.
  • baking (dry) film means heating the dry film from the “silver paste composition” of the present invention to a temperature required to form a “silver thin film”. Means.
  • the present invention provides a silver paste composition containing A) inorganic acid silver and Z or organic acid silver; B) an organic binder; and C) a solvent.
  • the silver paste composition of the present invention has a silver content power based on the total weight of the composition based on the total weight of the component A), regardless of what combination of component A) is inorganic acid silver and organic acid silver.
  • this silver paste composition has excellent printing characteristics on a substrate, and a stable and dense silver thin film is formed within a thickness range of 0.2 to 2.5 microns by heat drying and low temperature sintering. be able to.
  • the silver thin film thus obtained is useful as a thin film conductor for various electronic components (thin film electrodes of resistors) and a wiring material for display devices.
  • component A) when component A) is an inorganic acid silver alone, the silver content based on component A) is preferably 10 to 50% by weight based on the total weight of the composition. If the concentration of silver contained in the inorganic acid silver is 10% by weight or less, the film thickness after pyrolysis becomes too thin, and it is not preferable because the film density cannot be obtained. In addition, it is preferable to add a compound having a silver concentration exceeding 50% by weight because the ratio of the organic binder and the solvent to the inorganic acid silver is too small to be a paste suitable for screen printing.
  • the silver content based on the component is preferably 10 to 30% by weight based on the total weight of the composition.
  • the silver concentration in the organic acid silver is 10% by weight or less, the film thickness after thermal decomposition becomes too thin, and the film density cannot be obtained.
  • component A) is a mixture of inorganic acid silver and organic acid silver.
  • the printing characteristics on the substrate of the silver paste composition are excellent compared to the case of each of the inorganic acid silver or organic acid silver alone, and heat drying and After sintering, a very stable and dense silver thin film can be formed.
  • the amount of inorganic acid silver and organic acid silver can be freely combined depending on the materials used. From the viewpoint of the viscosity of a silver paste composition suitable for forming a silver thin film, inorganic acid silver is used.
  • the ratio of the weight of the organic acid silver to the total weight of the organic acid silver is 2 to 60 More preferably, it is 5% to 30%.
  • component A) is a mixture of inorganic acid silver and organic acid silver
  • the content power of silver based on component A) is 10 to 45% by weight based on the total weight of the composition. I like it. If the silver content in the paste is less than 10% by weight, the film thickness after pyrolysis becomes too thin, and the denseness of the film cannot be obtained. In addition, it is not preferable that the silver concentration exceeds 45% by weight because the ratio of the organic binder and the solvent in the paste is too small and the paste is not suitable for screen printing.
  • the silver paste composition of the present invention is substantially free of silver powder.
  • the metal silver particles of about 1 ⁇ m or less can be appropriately freed.
  • Examples of the inorganic acid silver used in the present invention include acid silver and silver carbonate.
  • a fatty acid As the organic acid silver used in the present invention, a fatty acid, an aromatic acid or a hydroxy acid is preferably used. In particular, when a fatty acid is used, C to C
  • Typical examples of silver include silver acetate, silver lactate, silver benzoate, silver 2-ethylhexanoate, silver oleate, and silver dodecyl mercaptan. Even in the form of powdered organic acid silver that does not necessarily need to be in a liquid state, it can be used because it can ensure dispersion stability.
  • the organic binder of component B) used in the present invention includes, but is not limited to, for example, ethyl cellulose resin, nitrocellulose resin, acrylic resin, terpene resin, and asphaltite.
  • asphaltite when asphaltite is included as a resin for organic binders, inorganic acid silver, or in particular, organic acid silver and asphaltite can be subjected to a chemical cross-linking reaction in the dispersion process by heating and mixing, and the dispersion stability of the paste Can be increased.
  • an alkali-soluble resin, a photocurable monomer, and photopolymerization start in an organic binder
  • an agent By including an agent, photo pattern formation by imparting photosensitivity is possible.
  • Examples of the solvent of component C) used in the present invention include, for example, relatively high boiling alcohol solvents (for example, terbineol and benzyl alcohol) and esters (for example, butyl) that dissolve at least part of the above components. Forces including, but not limited to, carbitol and trimethylpentanediol isomonobutyrate (abbreviation: TMP I).
  • relatively high boiling alcohol solvents for example, terbineol and benzyl alcohol
  • esters for example, butyl
  • TMP I trimethylpentanediol isomonobutyrate
  • the silver paste composition of the present invention is excellent in sinterability, the silver paste composition of the present invention needs to be fired at a high temperature of 500 ° C or higher (for example, when formed as an electrode of a resistor on an alumina substrate).
  • the firing temperature of the resistor is usually about 850 ° C, so the electrode formed prior to the resistor naturally passes through a thermal process of about 850 ° C.) It is necessary to control.
  • the silver paste composition of the present invention may contain a silver sintering inhibitor, if necessary, as such a silver sintering inhibitor, rhodium, noradium, platinum and ruthenium.
  • Group powers including, but not limited to, metal organic compounds or metal organic sulforesinates of at least one or more selected metals.
  • a sintering inhibitor based on the total weight of the silver paste composition in terms of sintering suppression effect. Addition of a content higher than this is not preferable because it causes an increase in resistance value and an increase in material cost, and is generally not desired as an electrode. If it is desired to control the sheet resistance of the electrode to be intentionally high, it is naturally possible to contain 1% by weight or more. In particular, palladium may be designed with a silver concentration of 5% by weight or more to prevent migration.
  • the conventional silver paste contains 1 to 2 glass powders.
  • the electrode thickness after firing may be around 1 m at most
  • glass powder having a particle distribution of about 1 to 5 ⁇ m is usually mixed and dispersed.
  • the particles are too large to form a dense film. Therefore, it is preferable to contain a metal organic material of at least one metal selected from bismuth, silicon, boron, lead, chromium, copper, and vanadium force.
  • These metal organic substances are generally liquid substances. Therefore, it can be easily dispersed in the paste and has excellent adhesion to substrates for typical electronic components such as glass substrates and alumina substrates.
  • inorganic acid silver and a solvent are blended in a predetermined amount and pre-stirred with a stirrer. After completion of stirring, an organic binder is added, and then dispersed with a three-roll roller or the like, and a solvent is added so as to obtain a predetermined viscosity characteristic.
  • the silver paste composition thus obtained is printed on a substrate.
  • a screen printing method, a nod printing method, a spray method, a dating method, a spin coating method, a brush coating method, and the like can be used, but not limited thereto.
  • screen printing for example, printing on a substrate with a screen of 325 mesh, emulsion thickness 10 ⁇ m, etc.
  • the thickness of the print coating film can be appropriately set in consideration of the silver concentration and the paste viscosity.
  • substrates to be printed and applied include, but are not limited to, glass substrates and ceramics.
  • a dry film having a predetermined thickness can be obtained by drying for a predetermined time at a temperature of about 90 to 150 ° C, preferably about 100 to 120 ° C. it can.
  • a sintered silver thin film can be obtained by further firing the dried film at a temperature of about 450 to 600 ° C, preferably about 500 ° C.
  • ceramic is used for the substrate, it is fired at a temperature of 550 to 900 ° C. At this time, for example, when the silver concentration in the silver paste composition is 30% by weight, a silver thin film having a thickness of about 1 ⁇ m is obtained.
  • the solvent contained in the silver paste composition according to the present invention has a boiling point of usually around 200 ° C, but most of the solvent component evaporates at the vapor pressure in the drying step after printing.
  • the organic vehicle is added to impart viscosity to the paste, but it is also thermally decomposed at a temperature of about 300 ° C to 400 ° C and disappears.
  • thermal decomposition starts from about 200 ° C., and thermal decomposition ends at about 360 ° C.
  • silver carbonate precipitates due to pyrolysis, and atomic silver particles are deposited. These particles start to sinter rapidly, but since silver sintering occurs in conjunction with the thermal decomposition of the organic binder and the thermal decomposition of silver carbonate, a thin film can be stably obtained. Also normal
  • the silver concentration of the silver paste composition is about 32 wt%, Pd concentration of about 0.4 wt%, Rh concentration of about 0.01 wt%, Bi concentration 0.045 Weight 0 / 0 .
  • the silver paste composition thus obtained was printed on a glass substrate with a stainless steel 325 mesh and an emulsion thickness of 10 ⁇ m, a high-definition electrode pattern with a pattern width of 80 ⁇ m and a space of 50 ⁇ could be printed. This is presumably because oleic acid and gyrsonite, a type of asphaltite, chemically cross-linked, resulting in a paste composition that does not bleed easily.
  • the film thickness after drying was 8 ⁇ m. Next, when this dried film was baked at 550 ° C, a 1.2 m silver thin film was obtained. The sheet resistance value of this electrode film was 25 ⁇ . The force of the peel test using a scotch tape on the silver thin film electrode obtained here did not peel at all. Furthermore, as a heat resistance test, the rate of change in the force resistance value after repeated baking at 600 ° C for 5 times was 5% or less, which was within the measurement error range.
  • the effects of the Rh and Pd metal organic substances are exemplified as the material for improving the heat resistance, but the effects are the same even when the platinum and Ru metal organic substances are used.
  • the same effect can also be obtained by adding force B or Pb metal organics that illustrate the effects of Bi, Si, Cr metal organic materials as materials to ensure adhesion to the substrate. Needless to say, you can do it.
  • inorganic silver 50 parts by weight of silver carbonate (silver concentration: 79.8% by weight) was used.
  • silver carbonate is a powdery substance, there are scattered lumps of agglomerated powder. Premixing is performed beforehand with a mixing and grinding machine, and the agglomerated powder is crushed, and then the terpene compound is used as an organic vehicle.
  • the silver paste composition according to the present invention was left to stand at room temperature of about 23 ° C for 1 week, and then printed and baked in the same manner. Concavities and convexities were observed on the film surface and the film surface after firing as compared with that immediately after kneading. As for the surface roughness, the force Rz immediately after kneading was about 0.2 m, whereas the one after one week had Rz of about 0.2. This is presumed to be due to reagglomeration of silver carbonate in the paste. By adding fatty acids such as stearic acid and oleic acid, reaggregation of silver carbonate could be suppressed.
  • fatty acids such as stearic acid and oleic acid
  • Example 2 a silver paste composition in which 1 part by weight of silver carbonate in Example is replaced with silver oleate will be described.
  • Silver carbonate (silver concentration: 79.8% by weight) as inorganic acid silver was reduced from 50 parts by weight to 44 parts by weight, and organic oleate (silver concentration: 27.7% by weight) 18 Part by weight was added. (The silver concentration after calcination is about 40% by weight as in Example 2.) Since both silver carbonate and silver oleate are powders, they are premixed in advance with a mixing grinder to break up the agglomerated powder, and then terpene abietic acid is used as an organic vehicle in the same manner as in Example 2.
  • Example 2 The strength of the paste composition after printing and baking after being left at about 23 ° C for 1 week. For this paste, no significant difference was observed in the surface roughness immediately after kneading and after standing for 1 week. . It is estimated that silver oleate contributed to the dispersion stability of the silver paste composition. The same effect is observed in common with organic acid silver such as silver acetate, silver lactate, silver dodecyl mercaptan, etc., but the molecular weight constituting the organic acid! / Silver oleate is most excellent in dispersion stability.
  • organic acid silver such as silver acetate, silver lactate, silver dodecyl mercaptan, etc.
  • a fine pattern printability was confirmed by printing on a glass substrate (PD200 manufactured by Asahi Glass) with a screen of 325 stainless mesh and emulsion thickness of 10 microns.
  • Pattern width Z space is the force that can print up to 75 microns. Where space is narrower than that, -Jimi partially connected the lines.
  • the viscosity characteristics of this paste were 420 pa's at one revolution of Brookfield rotary viscometer, 80.8 pa's at 10 revolutions, and the rotational viscosity ratio (viscosity of one revolution Z10 revolutions) was about 5. .
  • Viscosity characteristics of exactly what was heated and stirred at 150 ° C for 60 minutes is 2240 pa's for one revolution of Brookfield rotary viscometer, 188 pa's for 10 revolutions, and the rotational viscosity ratio (viscosity for one revolution Z10 viscosity for one revolution) Becomes about 12 and becomes a very thixotropic paste.
  • a paste with this viscosity characteristic is printed on a glass substrate (PD200 made by Asahi Glass) using a screen of 325 stainless mesh and emulsion thickness of 10 microns, and if the fine pattern printability is confirmed, the pattern width Z space can be printed up to 40 microns. did it.
  • the paste containing abietic acid or gilsonite has an excellent characteristic that the viscosity characteristic can be easily changed by a crosslinking reaction depending on the superheated stirring condition of the paste.
  • the dry film thickness was 8 microns. Furthermore, when fired at 600 ° C for 10 minutes, a silver thin film of about 1 micron was obtained.
  • the sheet resistance value was about 35 ⁇ ⁇ (specific resistance about 4 ⁇ ′cm).
  • the mixture was stirred for 150 minutes at 150 degrees with a stirrer. After cooling, about 11 parts by weight of terbinol was added as a viscosity adjusting solvent to adjust the viscosity of the paste. After printing on a glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) with a 400 stainless mesh, 8 micron emulsion screen, and drying at 120 ° C for 10 minutes, the dry film thickness was 6 microns.
  • PD200 manufactured by Asahi Glass Co., Ltd.
  • Orein silver as the organic acid silver (silver concentration: 27.7 wt 0/0) 15 parts by weight, 7.5 parts by weight of Girusoraito 35% solution dissolved in rosemary oil and an organic vehicle, sintering inhibitors and to Rh metal organic: metal organic substances (Rh concentration: 5 wt%) of 0.45 parts by weight of Pd (Pd concentration: 9. 55 weight 0/0) 1.
  • Rh concentration: 5 wt% 0.45 parts by weight of Pd (Pd concentration: 9. 55 weight 0/0) 1.
  • 46 wt parts, bismuth resinate as the glass component 1 part by weight of Bi concentration: 3.00% by weight was added. After all of these were blended, they were heated and stirred with a stirrer at 150 degrees for 30 minutes.
  • the viscosity of the paste was adjusted by adding about 3 parts by weight of terneol as a solvent for adjusting the viscosity.
  • This silver paste composition was printed on a glass substrate (PD200 manufactured by Asahi Glass) using a 325 stainless steel mesh, 10-micron emulsion screen, and dried at 120 ° C for 10 minutes, resulting in a dry film thickness of 8 microns. It was. Further, when fired at 600 ° C. for 10 minutes, a silver thin film of about 0.4 microns was obtained.
  • the sheet resistance value was about 420 m ⁇ (specific resistance: about 17 ⁇ ′ cm), and the film had a very high resistance value.
  • the fired film was refired at 600 ° C, it was disconnected in the second time. This is because the silver concentration of the silver paste composition in this comparative example is as low as about 17% by weight, and the film is separated into islands by accelerating the sintering of the film by firing, and eventually the disconnection state is reached. It is thought.
  • thinning of wiring electrodes and terminal electrodes of various electronic components can be formed with high accuracy and at low cost, which contributes to miniaturization and high accuracy of electronic components.
  • a thin film layer of a bus line electrode of a display portion called a front panel of a flat display panel or the like typified by a PDP is required.

Abstract

A silver paste composition which comprises A) a silver salt of an inorganic acid and/or a silver salt of organic acid, B) an organic binder, and C) a solvent, wherein the content of the silver derived from said component A) is 10 to 50 wt % relative to the total amount of said composition. The above silver paste composition is novel and can provide a silver thin film which has a thickness of 2.5 microns or less, is dense, is stable and exhibits a low sheet resistance value, and thus can be suitably used as a thin film conducting material for various electronic parts (a thin film electrode of a resistor) and a wiring material for a display device.

Description

明 細 書  Specification
銀ペースト組成物  Silver paste composition
技術分野  Technical field
[0001] 本発明は、各種電子部品の薄膜導体 (抵抗器の薄膜電極)およびディスプレイデ バイスの配線材料に用いられる銀薄膜を形成するための銀ペースト組成物に関する 。本発明はまた、上記銀ペースト組成物から銀薄膜を製造する方法に関する。本発 明はさらに、上記銀薄膜を含む電子部品用薄膜導体およびディスプレイ用配線材料 を提供する。  The present invention relates to a silver paste composition for forming a silver thin film used for a thin film conductor (resistor thin film electrode) of various electronic components and a wiring material of a display device. The present invention also relates to a method for producing a silver thin film from the silver paste composition. The present invention further provides a thin film conductor for electronic parts including the silver thin film and a wiring material for display.
背景技術  Background art
[0002] 近年の電子デバイスの技術的進展は目覚 、。  [0002] Technical development of electronic devices in recent years is remarkable.
[0003] 携帯電話の小型軽量ィ匕競争が激ィ匕する中で、電子デバイスそのものの小型軽量 化が必須となっている。これらの小型部品の実現に向け導体配線のパターン精度の 微細化および特性の向上の目的で電極の薄膜ィ匕の要求も強まっている。  [0003] Amid the intense competition for small and light cell phones, it is essential to reduce the size and weight of electronic devices themselves. In order to realize these small components, there is an increasing demand for thin film electrodes for the purpose of miniaturizing the pattern accuracy of conductor wiring and improving the characteristics.
[0004] 端子電極の薄膜化は、金属粉末と有機ビヒクルを混合した所謂厚膜電極によるスク リーン印刷では、安定に 2. 5ミクロン以下の膜厚を得ることは困難であり、通常真空 蒸着ゃスパッタにより、 Cr、 Ni, Cu等の金属薄膜を形成したのち、フォトレジストバタ ーン形成し、その開口部をエッチング法で除去することによる、薄膜パターン形成法 や、金の有機金属を含有するペーストを厚膜パターン印刷し、その後焼成により、金 を主成分とする薄膜を得る方法が知られている。（例えば、特許文献 1参照） しかしながら、真空技法による薄膜電極形成は、真空装置、露光装置等の高価な 設備が必要で、設備'プロセスコストが高くなる。一方金の金属有機物を用いた薄膜 電極パターン形成法は、パターン形成プロセスそのものは、安価な厚膜技法である 力 金を用いるためその材料コストが極めて割高で一部の高級なデバイスに採用さ れるにとどまっている。  [0004] The thinning of the terminal electrode is difficult to obtain with a so-called thick film electrode mixed with metal powder and an organic vehicle, and it is difficult to stably obtain a film thickness of 2.5 microns or less. After forming a metal thin film of Cr, Ni, Cu, etc. by sputtering, a photoresist pattern is formed, and the opening is removed by an etching method. There is known a method of obtaining a thin film mainly composed of gold by printing a paste with a thick film pattern and then baking the paste. (For example, refer to Patent Document 1) However, the formation of thin film electrodes by a vacuum technique requires expensive equipment such as a vacuum apparatus and an exposure apparatus, resulting in high equipment costs. On the other hand, the thin-film electrode pattern formation method using gold metal organics is used in some high-end devices because the pattern formation process itself uses power gold, which is an inexpensive thick film technique, and its material cost is extremely high. Stays on.
[0005] 金に代わる金属として銀粉を用いた薄膜形成用銀ペーストの開発が試みられてき たが、膜厚が 2. 5ミクロン以下の安定した薄膜を形成することは困難である。  [0005] Although attempts have been made to develop a silver paste for forming a thin film using silver powder as a metal instead of gold, it is difficult to form a stable thin film having a thickness of 2.5 microns or less.
[0006] また、金以外の金属有機物を主体とするペーストの開発も試みられてきた力 例え ば銀の有機金属のみでペーストイ匕はできても、ペースト中の銀の含有量が高々 15〜 20重量％前後にしかならず、印刷によるパターン形成後、 600°C〜850°C程度の温 度で焼成するときに銀の有機金属の熱分解により発生する原子状の Agの微粒子に よる強い焼結が生じることにより、焼成膜が島状に分離し、力えって膜が緻密にならな いため、シート抵抗値の大きなものしか形成できなカゝつた。実用最低限の抵抗値 (シ ート抵抗値1001110〜5001110 )を得る場合にも、焼結膜の安定ィ匕を図るため、やむ を得ず金の有機金属を混合することが必要になっていた。（例えば、特許文献 2参照[0006] Another example is the development of pastes mainly composed of metal organics other than gold. Even if the paste can be made with only silver organic metal, the silver content in the paste is only about 15-20% by weight. After the pattern is formed by printing, the temperature is about 600 ° C-850 ° C. When firing, strong sintering occurs due to the atomic Ag fine particles generated by pyrolysis of silver organometallic, and the fired film is separated into islands, so the film does not become dense. Only a sheet having a large sheet resistance value could be formed. Even when obtaining the lowest practical resistance value (sheet resistance value 1001110 to 5001110), it was unavoidable to mix gold organic metal to stabilize the sintered film. . (For example, see Patent Document 2)
) o ) o
[0007] このように、実用的なレベルまでにシート抵抗値が小さぐ膜厚 2. 5ミクロン以下の 安定した銀薄膜を安価な厚膜ペースト技法で得る技術は!、まだに存在せず、電子部 品の薄膜電極として非常に重要であり、その開発は渴望されている。  [0007] In this way, there is no technology to obtain a stable silver thin film with a thickness of 2.5 microns or less with a sheet resistance value small enough to a practical level by an inexpensive thick film paste technique! It is very important as a thin-film electrode for electronic components, and its development is envied.
[0008] またディスプレイデバイスの業界にぉ 、ては、 PDP (プラズマディスプレイパネル） の前面板のバスラインの導体は、その上部に形成される誘電体の信頼性の向上のた め、電極の薄膜ィ匕が求められている。更に大面積に電極形成するため、電極の厚み を薄くすることは、大幅なコストダウン（貴金属の消費量の低減）につながるため、極 めて有用であるにも係らず、未だ実現されて ヽな 、。  [0008] Also, in the display device industry, the bus line conductor on the front panel of a PDP (plasma display panel) is an electrode thin film for improving the reliability of the dielectric formed on the bus line conductor.匕 is required. In order to form an electrode in a larger area, reducing the thickness of the electrode leads to a significant cost reduction (reduction of precious metal consumption), so it has been realized even though it is extremely useful. Nah ...
特許文献 1：特開平 6—45118号公報  Patent Document 1: JP-A-6-45118
特許文献 2：特開平 4— 326791号公報  Patent Document 2: Japanese Patent Laid-Open No. 4-326791
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0009] 本発明の課題は、各種電子部品の薄膜導体 (抵抗器の薄膜電極)およびディスプ レイデバイスの配線材料に有用な 2. 5ミクロン以下の緻密で安定したシート抵抗値の 小さい銀薄膜を得るための、新しい銀ペースト組成物を提供することにある。  [0009] An object of the present invention is to provide a dense and stable silver thin film having a small sheet resistance value of 2.5 microns or less, which is useful as a thin film conductor (resistor thin film electrode) for various electronic components and a wiring material for a display device. It is to provide a new silver paste composition to obtain.
課題を解決するための手段  Means for solving the problem
[0010] 本発明者らは、鋭意研究を重ねた結果、無機酸銀および Zまたは有機酸銀と有機 ノインダと溶剤とを含有する銀ペースト組成物にぉ 、て、ペースト粘度の観点から、 無機酸銀および/または有機酸銀に基づく銀の含有量を制御することで、この銀べ 一スト組成物の基板上への印刷特性が優れ、加熱乾燥および低温焼結により 0. 2 〜2. 5ミクロンの膜厚範囲内で安定した緻密な銀薄膜を形成できることを見出し、上 記課題を解決した。 As a result of extensive research, the present inventors have found that a silver paste composition containing inorganic acid silver and Z or organic acid silver, an organic noder, and a solvent is inorganic from the viewpoint of paste viscosity. By controlling the silver content based on silver oxide and / or organic acid silver, the printing properties of this silver-based composition on the substrate are excellent, and 0.2% by heat drying and low-temperature sintering. We found that a stable and dense silver thin film can be formed within a thickness range of ~ 2.5 microns, and solved the above problems.
[0011] 本発明者らはまた、上記の銀薄膜が、各種電子部品の薄膜導体 (抵抗器の薄膜電 極)およびディスプレイデバイスの配線材料に有用であることを見出し、本発明を完 成した。  The inventors of the present invention have also found that the above-described silver thin film is useful for a thin film conductor (resistor thin film electrode) of various electronic components and a wiring material of a display device, thereby completing the present invention. .
[0012] このように、本発明では以下を提供する。  Thus, the present invention provides the following.
(1)以下の成分：  (1) The following ingredients:
A)無機酸銀および,または有機酸銀；  A) inorganic acid silver and / or organic acid silver;
B)有機バインダ;ならびに  B) organic binders; and
C)溶剤、  C) solvent,
を含有する銀ペースト組成物であって、  A silver paste composition comprising:
該成分 A)に基づく銀の含有量が、該組成物の全重量を基準として 10〜50重量％ である、銀ペースト組成物。  A silver paste composition, wherein the silver content based on component A) is from 10 to 50% by weight, based on the total weight of the composition.
(2)銀粉末を実質的に含有しない、項目（1)に記載の銀ペースト組成物。  (2) The silver paste composition according to item (1), which contains substantially no silver powder.
(3)上記無機酸銀は、酸ィ匕銀または炭酸銀である、項目（1)に記載の銀ペースト組 成物。  (3) The silver paste composition according to item (1), wherein the inorganic acid silver is acid silver or silver carbonate.
(4)上記有機酸銀は、酢酸銀、乳酸銀、ォレイン酸銀または安息香酸銀である、項 目（1)に記載の銀ペースト組成物。  (4) The silver paste composition according to item (1), wherein the organic acid silver is silver acetate, silver lactate, silver oleate or silver benzoate.
(5)上記成分 Α)は、無機酸銀と有機酸銀との混合物である、項目（1)に記載の銀べ 一スト組成物。  (5) The silver base composition according to item (1), wherein the component i) is a mixture of inorganic acid silver and organic acid silver.
(6)上記有機バインダは、ァスファルタイトである、項目（1)に記載の銀ペースト組成 物。  (6) The silver paste composition according to item (1), wherein the organic binder is asphaltite.
(7)上記有機バインダは、アルカリ可溶性榭脂、光硬化性モノマーおよび光重合開 始剤を含有する、項目（1)に記載の銀ペースト組成物。  (7) The silver paste composition according to item (1), wherein the organic binder contains an alkali-soluble resin, a photocurable monomer, and a photopolymerization initiator.
(8)追加の成分として、ロジウム、ノラジウム、白金およびルテニウム力もなる群力も選 択される少なくとも一種以上の金属の金属有機化合物または金属有機スルホレジネ ートをさらに含有する、項目（1)に記載の銀ペースト組成物。  (8) The item according to item (1), further comprising at least one metal-organic compound or metal-organic sulforesinate of at least one metal selected as a group power including rhodium, noradium, platinum, and ruthenium power as an additional component Silver paste composition.
(9)項目（1)に記載の銀ペースト組成物力 得られる厚み 0. 2〜2. 5 mの銀薄膜 (10)項目（9)に記載の銀薄膜を含む、電子部品用薄膜導体。 (9) Silver paste composition strength according to item (1) Obtained thin silver film having a thickness of 0.2 to 2.5 m (10) A thin film conductor for electronic parts, comprising the silver thin film according to item (9).
(11)項目（9)に記載の銀薄膜を含む、ディスプレイデバイス用配線材料。  (11) A display device wiring material comprising the silver thin film according to item (9).
(12)以下の工程：  (12) The following steps:
a)無機酸銀および Zまたは有機酸銀と有機ノインダと溶剤とを含有する銀ペースト 組成物の膜を基板上に形成する工程；  a) forming a film of a silver paste composition containing inorganic acid silver and Z or organic acid silver, an organic noinda and a solvent on a substrate;
b)該膜を乾燥する工程；および  b) drying the membrane; and
c)該乾燥膜を焼成する工程、  c) firing the dry film,
を包含する、銀薄膜の製造方法。  A method for producing a silver thin film.
(13)上記工程 a)は、スクリーン印刷によって行われる、項目（12)に記載の方法。 (13) The method according to item (12), wherein step a) is performed by screen printing.
(14)上記工程 b)は、 90〜150°Cで行われる、項目（12)に記載の方法。 (14) The method according to item (12), wherein the step b) is performed at 90 to 150 ° C.
(15)上記工程 c)は、 450〜700°Cで行われる、項目（12)に記載の方法。  (15) The method according to item (12), wherein step c) is performed at 450 to 700 ° C.
(16)項目（12)に記載の方法によって得られる、厚み 0. 2〜2. の銀薄膜。 発明の効果  (16) A silver thin film having a thickness of 0.2 to 2. obtained by the method according to item (12). The invention's effect
[0013] 本発明によれば、導電性の優れた銀薄膜をスクリーン印刷等の厚膜技法でパター ンユングでき、また焼成により、 0. 2〜2. 5 m程度の銀薄膜を各種基板上に密着 性良く得ること可能である。また、各種用途に対応し焼成温度が 450°C程度の低温 から、 850°C程度の高温の焼成に耐えうるように焼結抑制剤も適宜添加することで、 膜の耐熱安定性を確保された銀薄膜電極を提供させることができる。  [0013] According to the present invention, a silver thin film having excellent conductivity can be patterned by a thick film technique such as screen printing, and a silver thin film of about 0.2 to 2.5 m can be formed on various substrates by firing. It is possible to obtain good adhesion. In addition, the heat resistance of the film can be ensured by adding a sintering inhibitor as appropriate so that it can withstand baking at temperatures as low as 450 ° C or as high as 850 ° C. A silver thin film electrode can be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 以下、本発明を説明する。本明細書の全体にわたり、単数形の表現は、特に言及 しない限り、その複数形の概念をも含むことが理解されるべきである。また、本明細書 において使用される用語は、特に言及しない限り、当該分野で通常用いられる意味 で用いられることが理解されるべきである。  [0014] Hereinafter, the present invention will be described. Throughout this specification, it should be understood that expression in the singular also includes the concept of the plural unless specifically stated otherwise. In addition, it is to be understood that the terms used in this specification are used in the meaning normally used in the art unless otherwise specified.
[0015] (用語）  [0015] (Terminology)
以下に本明細書において特に使用される用語の定義を列挙する。  Listed below are definitions of terms particularly used in the present specification.
[0016] 本明細書において「銀ペースト組成物」とは、組成物中に含まれる金属成分のうち 銀が最も多く存在し、かつ下記で定義する「基板」上に塗布した際に膜を形成し得る ペースト状の組成物を意味し、上記規定を満たすものであれば、この組成物を構成 する各成分の種類および量は特に制限されな 、。この「銀ペースト組成物」との用語 は、本明細書中において、「銀ペースト」との用語と互換可能に使用される。 In the present specification, the “silver paste composition” means that silver is the most among the metal components contained in the composition, and a film is formed when applied on a “substrate” defined below. Can As long as it means a paste-like composition and satisfies the above requirements, the type and amount of each component constituting the composition are not particularly limited. The term “silver paste composition” is used herein interchangeably with the term “silver paste”.
[0017] 本明細書において「無機酸銀」とは、無機酸 (Cl、 S、 N、 Pなどの非金属を含む酸 基が水素と結合してできた酸)の銀塩を意味し、代表例として炭酸銀および酸化銀な どが挙げられる。  [0017] As used herein, "inorganic acid silver" means a silver salt of an inorganic acid (an acid group formed by combining an acid group containing a nonmetal such as Cl, S, N, and P with hydrogen), Typical examples include silver carbonate and silver oxide.
[0018] 本明細書において「有機酸銀」とは、上記「無機酸銀」に対する用語であり、分子内 に 1個以上のカルボキシル基（-COOH)を含む有機酸 (例えば、脂肪酸、芳香族酸 、ヒドロキシ酸など)の銀塩を意味する。本発明における「脂肪酸」とは、カルボキシル 基 1個をもつ R—COOH (Rは疎水鎖を表す)のうち、直鎖または分枝鎖の、飽和ま たは不飽和の鎖式構造をもつものの総称をいう。本発明で使用される脂肪酸の炭素 数は、特に制限されないが、一般に工業的に使用される C〜C の脂肪酸が本発明  In the present specification, the “organic acid silver” is a term for the above “inorganic acid silver”, and an organic acid containing one or more carboxyl groups (—COOH) in the molecule (for example, fatty acid, aromatic Acid or hydroxy acid). In the present invention, “fatty acid” refers to an R—COOH having one carboxyl group (where R represents a hydrophobic chain) having a linear or branched, saturated or unsaturated chain structure. A general term. The carbon number of the fatty acid used in the present invention is not particularly limited, but C to C fatty acids generally used industrially are the present invention.
1 31  1 31
で用いられる。少なくとも化学大辞典 4 共立出版株式会社 1989年縮刷版第 32刷 発行の第 492頁に列挙されている代表化合物は、本発明における脂肪酸として使用 可能である。本発明における「芳香族酸」とは、芳香族環に 1個以上のカルボキシル 基が置換したィ匕合物の総称をいい、代表的な例として、安息香酸などが挙げられる。 本発明における「ヒドロキシ酸」とは、分子内に— OH基と— COOHをもつ有機化合 物の総称をいい、代表的な例として、乳酸などが挙げられる。  Used in At least the representative compounds listed on page 492 of Kyoritsu Shuppan 4 Kyoritsu Shuppan Co., Ltd., 1989, Reprinted Edition 32nd Edition, can be used as fatty acids in the present invention. The “aromatic acid” in the present invention is a general term for compounds in which one or more carboxyl groups are substituted on the aromatic ring. Typical examples include benzoic acid. “Hydroxy acid” in the present invention is a general term for organic compounds having —OH group and —COOH in the molecule, and typical examples include lactic acid.
[0019] 本明細書において「有機バインダ」とは、本発明の銀ペースト組成物を基板上に塗 布して形成される膜の安定性および強度を確実にする目的で、銀ペースト組成物中 に含有される有機化合物を意味する。  In the present specification, the “organic binder” is used in the silver paste composition for the purpose of ensuring the stability and strength of a film formed by coating the silver paste composition of the present invention on a substrate. Means an organic compound contained in
[0020] 本明細書にぉ 、て「溶剤」とは、本発明の銀ペースト組成物を構成する各成分を完 全にまたは少なくとも一部溶解し、本発明の「銀ペースト組成物」にペーストとしての 適度な粘度を与えるような工業的に一般に使用される有機溶媒全てを指す。  In the present specification, the term “solvent” means that the components constituting the silver paste composition of the present invention are completely or at least partially dissolved, and the paste is added to the “silver paste composition” of the present invention. It refers to all organic solvents commonly used in the industry that give moderate viscosity as.
[0021] 本明細書にぉ ヽて「有機ビヒクル」とは、有機バインダを溶剤に溶解させたものを意 味する。  In the present specification, the “organic vehicle” means a solution in which an organic binder is dissolved in a solvent.
[0022] 本明細書にぉ 、て「 (成分 A) )に基づく銀の含有量」とは、成分 A)、つまり上で定 義した無機酸銀および Zまたは有機酸銀に由来する銀であって、本明細書中にお いて特に言及されない限り本発明の銀ペースト組成物に含まれることが意図されない 他の銀成分 (銀粉、銀粒子、銀微粒子、銀片など)または銀ィ匕合物に由来する銀で はない、銀の含有量を意味する。 [0022] As used herein, the term "silver content based on (component A))" refers to component A), that is, silver derived from inorganic acid silver and Z or organic acid silver as defined above. In this specification, Unless otherwise specified, it is not intended to be included in the silver paste composition of the present invention, and is not silver derived from other silver components (silver powder, silver particles, silver fine particles, silver pieces, etc.) or silver compounds, Means the silver content.
[0023] 本明細書において「銀粉末」とは、本明細書中において特に言及されない限り、本 発明の銀ペースト組成物に含まれることが意図されず、従来の導電性薄膜形成用銀 ペーストに含まれていた比較的粒径の大きな銀成分 (例えば、銀粉、銀粒子、銀微粒 子、銀片などが代表されるが、その形状は特に制限されない)を意味する。  [0023] In this specification, "silver powder" is not intended to be included in the silver paste composition of the present invention unless otherwise specified in the present specification, and is a conventional silver paste for forming a conductive thin film. It means a silver component having a relatively large particle diameter (for example, silver powder, silver particles, silver fine particles, silver pieces, etc., although the shape is not particularly limited).
[0024] 本明細書にぉ 、て「 (銀粉末を)実質的に含有しな 、」とは、本発明の「銀ペースト 組成物」から銀薄膜を形成させる際に、銀原子の安定した緻密な膜の形成を阻害す る量または悪影響を及ぼす量の上記「銀粉末」を、本発明の銀ペースト組成物が含ま ないことを意味する。  In the present specification, “substantially does not contain (silver powder)” means that when a silver thin film is formed from the “silver paste composition” of the present invention, silver atoms are stabilized. It means that the silver paste composition of the present invention does not contain the above “silver powder” in an amount that inhibits the formation of a dense film or has an adverse effect.
[0025] 本明細書において「銀薄膜」とは、本発明の「銀ペースト組成物」から本発明の方法 により形成された、安定でかつ緻密な厚み 2. 5ミクロン以下の銀薄膜を意味する。本 明細書中で特に言及されない限り、従来の銀薄膜とは区別される。  In the present specification, the “silver thin film” means a stable and dense silver thin film having a thickness of 2.5 μm or less formed from the “silver paste composition” of the present invention by the method of the present invention. . Unless otherwise stated in this specification, it is distinguished from conventional silver thin films.
[0026] 本明細書において「基板」とは、その上に塗布される本発明の「銀ペースト組成物」 の塗布性の点で、「銀ペースト組成物」と相性の良いものであれば何でもよぐ「基板」 の材質および形状は特に制限されない。  [0026] In the present specification, the "substrate" is anything that is compatible with the "silver paste composition" in terms of the applicability of the "silver paste composition" of the present invention applied thereon. The material and shape of the “substrate” are not particularly limited.
[0027] 本明細書において「(銀ペースト組成物の)膜」とは、本発明の「銀ペースト組成物」 が「基板」上に塗布され形成された膜を意味する。  In the present specification, the “film (of silver paste composition)” means a film formed by applying the “silver paste composition” of the present invention on a “substrate”.
[0028] 本明細書にぉ 、て「膜を乾燥する」とは、上で定義した「 (銀ペースト組成物の)膜」 から、溶剤の少なくとも一部を揮発させることを意味する。  In the present specification, “drying the film” means volatilizing at least a part of the solvent from the “film (of the silver paste composition)” defined above.
[0029] 本明細書において「（乾燥)膜を焼成する」とは、本発明の「銀ペースト組成物」から 「銀薄膜」を形成するのに必要な温度まで、上記乾燥膜を加熱することを意味する。  In the present specification, “baking (dry) film” means heating the dry film from the “silver paste composition” of the present invention to a temperature required to form a “silver thin film”. Means.
[0030] (好ま 、実施形態の説明）  [0030] (Preferably, description of the embodiment)
以下に、本発明の好ましい実施形態について説明する。以下に提供される実施形 態は、本発明のよりよい理解のために提供されるものであり、本発明の範囲は以下の 記載に限定されるべきでないことが理解される。従って、当業者は、本明細書中の記 載を参酌して、本発明の範囲内で適宜改変を行うことができることは明らかである。 [0031] 1つの局面において、本発明は、 A)無機酸銀および Zまたは有機酸銀; B)有機バ インダ;ならびに C)溶剤、を含有する銀ペースト組成物を提供する。本発明の銀ぺー スト組成物は、成分 A)が無機酸銀と有機酸銀とがどのような組み合わせであろうと、 成分 A)に基づく銀の含有量力 組成物の全重量を基準として 10〜50重量％である ことを特徴としている。これによつて、この銀ペースト組成物の基板上への印刷特性が 優れ、加熱乾燥および低温焼結により 0. 2〜2. 5ミクロンの膜厚範囲内で安定した 緻密な銀薄膜を形成することができる。また、このようにして得られた銀薄膜は、各種 電子部品の薄膜導体 (抵抗器の薄膜電極)およびディスプレイデバイスの配線材料 に有用である。 Hereinafter, preferred embodiments of the present invention will be described. The embodiments provided below are provided for a better understanding of the present invention, and it is understood that the scope of the present invention should not be limited to the following description. Therefore, it is obvious that those skilled in the art can make appropriate modifications within the scope of the present invention with reference to the description in the present specification. [0031] In one aspect, the present invention provides a silver paste composition containing A) inorganic acid silver and Z or organic acid silver; B) an organic binder; and C) a solvent. The silver paste composition of the present invention has a silver content power based on the total weight of the composition based on the total weight of the component A), regardless of what combination of component A) is inorganic acid silver and organic acid silver. It is characterized by 50% by weight. As a result, this silver paste composition has excellent printing characteristics on a substrate, and a stable and dense silver thin film is formed within a thickness range of 0.2 to 2.5 microns by heat drying and low temperature sintering. be able to. The silver thin film thus obtained is useful as a thin film conductor for various electronic components (thin film electrodes of resistors) and a wiring material for display devices.
[0032] 特に、成分 A)が無機酸銀単独である場合、成分 A)に基づく銀の含有量が、組成 物の全重量を基準として 10〜50重量％であることが好ましい。無機酸銀に含まれる 銀濃度が 10重量％以下である場合、熱分解後の膜厚が薄くなり過ぎて、膜の緻密 性が得られないため、好ましくない。また銀濃度が 50重量％を超えるような配合を行 おうとすると、無機酸銀に対する、有機バインダと溶剤の割合が少なすぎて、スクリー ン印刷に適するペースト状とならな 、ため、好ましくな 、。  [0032] In particular, when component A) is an inorganic acid silver alone, the silver content based on component A) is preferably 10 to 50% by weight based on the total weight of the composition. If the concentration of silver contained in the inorganic acid silver is 10% by weight or less, the film thickness after pyrolysis becomes too thin, and it is not preferable because the film density cannot be obtained. In addition, it is preferable to add a compound having a silver concentration exceeding 50% by weight because the ratio of the organic binder and the solvent to the inorganic acid silver is too small to be a paste suitable for screen printing.
[0033] 特に、成分 が有機酸銀単独である場合、成分 に基づく銀の含有量が、組成 物の全重量を基準として 10〜30重量％であることが好ましい。有機酸銀に含まれる 銀濃度が 10重量％以下である場合、熱分解後の膜厚が薄くなり過ぎて、膜の緻密 性が得られないため、好ましくない。また銀濃度が 30重量％を超えるような配合を行 おうとすると、有機酸銀に対する、有機バインダと溶剤の割合が少なすぎて、スクリー ン印刷に適するペースト状とならな 、ため、好ましくな 、。  [0033] In particular, when the component is an organic acid silver alone, the silver content based on the component is preferably 10 to 30% by weight based on the total weight of the composition. When the silver concentration in the organic acid silver is 10% by weight or less, the film thickness after thermal decomposition becomes too thin, and the film density cannot be obtained. In addition, it is preferable to add a compound having a silver concentration exceeding 30% by weight because the ratio of the organic binder and the solvent to the organic acid silver is too small to form a paste suitable for screen printing.
[0034] 好ま 、実施形態にぉ 、て、成分 A)は、無機酸銀と有機酸銀との混合物である。  [0034] Preferably, according to the embodiment, component A) is a mixture of inorganic acid silver and organic acid silver.
無機酸銀と有機酸銀との混合物を採用することにより、無機酸銀または有機酸銀そ れぞれ単独の場合に比べ、銀ペースト組成物の基板上への印刷特性が優れ、加熱 乾燥および焼結後、非常に安定した緻密な銀薄膜を形成することができる。無機酸 銀と有機酸銀との配合量は、それぞれ使用する材料によって自由に組み合わせるこ とができるが、銀薄膜を形成するのに適した銀ペースト組成物の粘度の観点から、無 機酸銀と有機酸銀との総重量に対する該有機酸銀の重量の占める割合は、 2〜60 %であることが好ましぐより好ましくは、 5〜30%である。 By adopting a mixture of inorganic acid silver and organic acid silver, the printing characteristics on the substrate of the silver paste composition are excellent compared to the case of each of the inorganic acid silver or organic acid silver alone, and heat drying and After sintering, a very stable and dense silver thin film can be formed. The amount of inorganic acid silver and organic acid silver can be freely combined depending on the materials used. From the viewpoint of the viscosity of a silver paste composition suitable for forming a silver thin film, inorganic acid silver is used. The ratio of the weight of the organic acid silver to the total weight of the organic acid silver is 2 to 60 More preferably, it is 5% to 30%.
[0035] また、このように成分 A)が無機酸銀と有機酸銀との混合物である場合、成分 A)に 基づく銀の含有量力 組成物の全重量を基準として 10〜45重量％であることが好ま しい。ペースト中の銀の含有量が 10重量％を下回ると、熱分解後の膜厚が薄くなり 過ぎて、膜の緻密性が得られないため、好ましくない。また銀濃度が 45重量％を超え るような配合を行おうとすると、ペースト中の有機バインダと溶剤の割合が少なすぎて 、スクリーン印刷に適するペースト状とならないため、好ましくない。  [0035] Further, when component A) is a mixture of inorganic acid silver and organic acid silver, the content power of silver based on component A) is 10 to 45% by weight based on the total weight of the composition. I like it. If the silver content in the paste is less than 10% by weight, the film thickness after pyrolysis becomes too thin, and the denseness of the film cannot be obtained. In addition, it is not preferable that the silver concentration exceeds 45% by weight because the ratio of the organic binder and the solvent in the paste is too small and the paste is not suitable for screen printing.
[0036] 1つの実施形態において、本発明の銀ペースト組成物は、銀粉末を実質的に含有 しない。これによつて、従来の導電性薄膜形成用銀ペーストでは達成し得なかった 2 . 5ミクロン以下の非常に薄く安定した銀薄膜を提供することができる。しかし、必要に 応じて、銀の薄膜形成を阻害しない限り、約 1 μ m程度以下の金属銀微粒子を適宜 カロ免ることちでさる。  [0036] In one embodiment, the silver paste composition of the present invention is substantially free of silver powder. As a result, it is possible to provide a very thin and stable silver thin film of 2.5 microns or less that could not be achieved by the conventional silver paste for forming a conductive thin film. However, if necessary, as long as the silver thin film formation is not hindered, the metal silver particles of about 1 μm or less can be appropriately freed.
[0037] 本発明で用いる無機酸銀として、例えば、酸ィ匕銀および炭酸銀などが挙げられるが [0037] Examples of the inorganic acid silver used in the present invention include acid silver and silver carbonate.
、これらに限定されない。 However, it is not limited to these.
[0038] 本発明で用いる有機酸銀として、脂肪酸、芳香族酸またはヒドロキシ酸が好んで使 用され、特に脂肪酸を使用する場合、 C〜C [0038] As the organic acid silver used in the present invention, a fatty acid, an aromatic acid or a hydroxy acid is preferably used. In particular, when a fatty acid is used, C to C
1 25の直鎖の飽和または不飽和の脂肪酸 が好ましぐ C〜C の直鎖の不飽和脂肪酸がより好ましい。本発明で用いる有機酸  125 linear saturated or unsaturated fatty acids are preferred C to C linear unsaturated fatty acids are more preferred. Organic acids used in the present invention
2 20  2 20
銀の代表例として、例えば、酢酸銀、乳酸銀、安息香酸銀、 2—ェチルへキサン酸銀 、ォレイン酸銀、ドデシルメルカブタン銀などが挙げられる。必ずしも液状である必要 はなぐ粉末状の有機酸銀であっても分散安定性は確保できるため、使用可能であ る。  Typical examples of silver include silver acetate, silver lactate, silver benzoate, silver 2-ethylhexanoate, silver oleate, and silver dodecyl mercaptan. Even in the form of powdered organic acid silver that does not necessarily need to be in a liquid state, it can be used because it can ensure dispersion stability.
[0039] 本発明で用いる成分 B)の有機バインダとして、例えば、ェチルセルロース榭脂、二 トロセルロース樹脂、アクリル榭脂、テルペン類の榭脂およびァスファルタイトなどが 挙げられる力 これらに限定されない。特に、有機バインダの榭脂としてァスファルタ イトを含有させた場合、無機酸銀または、特に有機酸銀とァスファルタイトが加熱混合 による分散過程で、化学的架橋反応することも出来、更にペーストの分散安定性を 増すことちできる。  [0039] The organic binder of component B) used in the present invention includes, but is not limited to, for example, ethyl cellulose resin, nitrocellulose resin, acrylic resin, terpene resin, and asphaltite. In particular, when asphaltite is included as a resin for organic binders, inorganic acid silver, or in particular, organic acid silver and asphaltite can be subjected to a chemical cross-linking reaction in the dispersion process by heating and mixing, and the dispersion stability of the paste Can be increased.
[0040] また、有機バインダに、アルカリ可溶性榭脂、光硬化性モノマーおよび光重合開始 剤を含有させることにより、光感光性の付与によるフォトパターン形成が可能となる。 [0040] In addition, an alkali-soluble resin, a photocurable monomer, and photopolymerization start in an organic binder By including an agent, photo pattern formation by imparting photosensitivity is possible.
[0041] 本発明で用いる成分 C)の溶剤として、例えば、上記成分を少なくとも一部溶解する 比較的高沸点のアルコール系溶剤（例えば、テルビネオールおよびべンジルアルコ ールなど）およびエステル類（例えば、ブチルカルビトールおよびトリメチルペンタンジ オールイソモノブチレート（略称: T. M. P. I)など）が挙げられる力 これらに限定さ れない。  [0041] Examples of the solvent of component C) used in the present invention include, for example, relatively high boiling alcohol solvents (for example, terbineol and benzyl alcohol) and esters (for example, butyl) that dissolve at least part of the above components. Forces including, but not limited to, carbitol and trimethylpentanediol isomonobutyrate (abbreviation: TMP I).
[0042] また、本発明の銀ペースト組成物は、焼結性に優れるため、 500°C以上の高温で 焼成することが必要な用途 (例えば、アルミナ基板上に抵抗体の電極として形成する 場合などは、抵抗体の焼成温度が通常 850°C程度であるため、抵抗体に先立って 形成される電極も当然 850°C程度の熱プロセスを通過する。）の場合、銀の焼結を抑 制する必要がある。  [0042] Further, since the silver paste composition of the present invention is excellent in sinterability, the silver paste composition of the present invention needs to be fired at a high temperature of 500 ° C or higher (for example, when formed as an electrode of a resistor on an alumina substrate). In this case, the firing temperature of the resistor is usually about 850 ° C, so the electrode formed prior to the resistor naturally passes through a thermal process of about 850 ° C.) It is necessary to control.
[0043] 従って、本発明の銀ペースト組成物は、必要に応じて、銀の焼結抑制剤を含んでも 良ぐこのような銀の焼結抑制剤として、ロジウム、ノラジウム、白金およびルテニウム 力 なる群力 選択される少なくとも一種以上の金属の金属有機化合物または金属 有機スルホレジネートなどが挙げられる力 これらに限定されな 、。  [0043] Therefore, the silver paste composition of the present invention may contain a silver sintering inhibitor, if necessary, as such a silver sintering inhibitor, rhodium, noradium, platinum and ruthenium. Group powers including, but not limited to, metal organic compounds or metal organic sulforesinates of at least one or more selected metals.
[0044] 材料構成によって異なるが、焼結抑制効果の点で、銀ペースト組成物の全重量を 基準として、 0. 01〜1重量％の焼結抑制剤を添加することが好ましい。これ以上の 含有量を添加すると、抵抗値の上昇と材料コストの上昇を招き、電極としては一般に 望まれないため、好ましくない。電極のシート抵抗値を意図的に高めにコントロールし たい場合は、 1重量％以上含有させることも当然可能である。特にパラジウムについ ては、マイグレーション防止のため、銀に対する濃度を 5重量％以上に設計する場合 もあり得る。  [0044] Although different depending on the material structure, it is preferable to add 0.01 to 1% by weight of a sintering inhibitor based on the total weight of the silver paste composition in terms of sintering suppression effect. Addition of a content higher than this is not preferable because it causes an increase in resistance value and an increase in material cost, and is generally not desired as an electrode. If it is desired to control the sheet resistance of the electrode to be intentionally high, it is naturally possible to contain 1% by weight or more. In particular, palladium may be designed with a silver concentration of 5% by weight or more to prevent migration.
[0045] また各種基材に密着性を持たせるため、従来の銀ペーストには、ガラス粉末を 1〜  [0045] In order to provide adhesion to various base materials, the conventional silver paste contains 1 to 2 glass powders.
5重量％程度添加していた力 本発明においては、焼成後の電極厚みが高々 1 m 前後の場合もあるため、通常 1〜5 μ m程度の粒子分布を持つガラス粉末を混合分 散させるのは粒子が大きすぎて緻密な成膜ができない。従って、ビスマス、シリコン、 ホウ素、鉛、クロム、銅、バナジウム力 選ばれる少なくとも一種以上の金属の金属有 機物を含有させることが好ましい。これらの金属有機物は、一般に液状物質であるた め、ペースト中への分散も容易で、またガラス基板、アルミナ基板等の代表的電子部 品用の基板に対する密着性に優れるものである。 In the present invention, since the electrode thickness after firing may be around 1 m at most, glass powder having a particle distribution of about 1 to 5 μm is usually mixed and dispersed. The particles are too large to form a dense film. Therefore, it is preferable to contain a metal organic material of at least one metal selected from bismuth, silicon, boron, lead, chromium, copper, and vanadium force. These metal organic substances are generally liquid substances. Therefore, it can be easily dispersed in the paste and has excellent adhesion to substrates for typical electronic components such as glass substrates and alumina substrates.
[0046] 以下に、本発明の銀ペースト組成物の調製方法および銀薄膜の製造方法につい て、説明する。  [0046] Hereinafter, a method for preparing the silver paste composition of the present invention and a method for producing a silver thin film will be described.
[0047] まず、無機酸銀と溶剤とを所定の量で配合し、撹拌機で予備攪拌する。攪拌終了 後、有機バインダーを加えたのち、三本ロール等で分散させ、さらに所定の粘度特性 になるように溶剤を添加する。  [0047] First, inorganic acid silver and a solvent are blended in a predetermined amount and pre-stirred with a stirrer. After completion of stirring, an organic binder is added, and then dispersed with a three-roll roller or the like, and a solvent is added so as to obtain a predetermined viscosity characteristic.
[0048] 次いで、こうして得られた銀ペースト組成物を基板上に印刷塗布する。この印刷塗 布には、スクリーン印刷法、ノッド印刷法、スプレー法、デイツビング法、スピンコーテ イング法、筆塗り法などを用いることができるが、これらに限定されない。電子部品の 薄膜導体用銀薄膜を調製する場合は、スクリーン印刷 (例えば 325メッシュ、乳剤厚 10 μ m等のスクリーンにて基板上に印刷する）が特に好ましい。この印刷塗布膜の 厚みは、銀濃度およびペースト粘度を考慮して、適宜設定され得る。  [0048] Next, the silver paste composition thus obtained is printed on a substrate. For this printing coating, a screen printing method, a nod printing method, a spray method, a dating method, a spin coating method, a brush coating method, and the like can be used, but not limited thereto. When preparing a silver thin film for a thin film conductor of an electronic component, screen printing (for example, printing on a substrate with a screen of 325 mesh, emulsion thickness 10 μm, etc.) is particularly preferable. The thickness of the print coating film can be appropriately set in consideration of the silver concentration and the paste viscosity.
[0049] 印刷塗布される基板としては、ガラス基板およびセラミックなどが挙げられるが、これ らに限定されない。  [0049] Examples of substrates to be printed and applied include, but are not limited to, glass substrates and ceramics.
[0050] 基板上に印刷塗布後、一般的に、 90〜150°C、好ましくは 100〜120°C程度の温 度で、所定時間乾燥することにより、所定の厚みの乾燥膜を得ることができる。ガラス 基板の場合、その乾燥膜をさらに 450〜600°C、好ましくは 500°C程度の温度で焼 成することで、銀の焼結薄膜が得られる。基板にセラミックを用いる場合は、 550〜9 00°Cの温度で焼成される。このとき、例えば、銀ペースト組成物中の銀濃度が 30重 量％の場合、銀の厚みは約 1 μ m程度の銀薄膜となる。  [0050] After printing on the substrate, generally, a dry film having a predetermined thickness can be obtained by drying for a predetermined time at a temperature of about 90 to 150 ° C, preferably about 100 to 120 ° C. it can. In the case of a glass substrate, a sintered silver thin film can be obtained by further firing the dried film at a temperature of about 450 to 600 ° C, preferably about 500 ° C. When ceramic is used for the substrate, it is fired at a temperature of 550 to 900 ° C. At this time, for example, when the silver concentration in the silver paste composition is 30% by weight, a silver thin film having a thickness of about 1 μm is obtained.
[0051] 以下に、銀の薄膜が得られるメカニズムを説明する。  [0051] Hereinafter, a mechanism for obtaining a silver thin film will be described.
[0052] 本発明による銀ペースト組成物に含まれる溶剤は沸点が通常 200°C前後のものが 使用されるが、溶剤成分は、印刷後の乾燥工程で、その蒸気圧で大半が蒸発する。 有機ビヒクルは、ペーストに粘性を与えるために添加されるが、これも通常 300°C〜4 00°C程度の温度で熱分解され消失する。銀の無機酸は、例えば炭酸銀の場合、 20 0°C程度から熱分解が開始され、 360°C程度で熱分解が終了する。熱分解終了時に は、銀の炭酸塩が熱分解により、原子状銀粒子が析出するが、これらの超微細な銀 の粒子が急速に焼結を開始するが、有機バインダの熱分解と炭酸銀との熱分解に連 動して銀の焼結が起こるため、薄い皮膜を安定に得ることが可能である。また通常の[0052] The solvent contained in the silver paste composition according to the present invention has a boiling point of usually around 200 ° C, but most of the solvent component evaporates at the vapor pressure in the drying step after printing. The organic vehicle is added to impart viscosity to the paste, but it is also thermally decomposed at a temperature of about 300 ° C to 400 ° C and disappears. In the case of silver inorganic acid, for example, in the case of silver carbonate, thermal decomposition starts from about 200 ° C., and thermal decomposition ends at about 360 ° C. At the end of pyrolysis, silver carbonate precipitates due to pyrolysis, and atomic silver particles are deposited. These particles start to sinter rapidly, but since silver sintering occurs in conjunction with the thermal decomposition of the organic binder and the thermal decomposition of silver carbonate, a thin film can be stably obtained. Also normal
1 μ m程度の銀の金属粒子を用いる場合に比較し、圧倒的に焼結が早ぐ有機バイ ンダの熱分解終了温度との兼ね合 、もあるが、 400°C〜500°C程度で十分焼結させ ることがでさる。 Compared to the case of using silver metal particles of about 1 μm, there is a trade-off with the thermal decomposition end temperature of the organic binder, which is overwhelmingly faster, but at around 400 ° C to 500 ° C. It can be fully sintered.
[0053] 本明細書において引用された、科学文献、特許、特許出願などの参考文献は、そ の全体が、各々具体的に記載されたのと同じ程度に本明細書において参考として援 用される。  [0053] References such as scientific literature, patents and patent applications cited herein are incorporated herein by reference to the same extent as if each was specifically described. The
[0054] 以上のように、本発明の好ましい実施形態を用いて本発明を例示してきた力 本発 明は、この実施形態に限定して解釈されるべきものではない。本発明は、特許請求 の範囲によってのみその範囲が解釈されるべきであることが理解される。当業者は、 本発明の具体的な好ましい実施形態の記載から、本発明の記載および技術常識に 基づいて等価な範囲を実施することができることが理解される。本明細書において引 用した特許、特許出願および文献は、その内容自体が具体的に本明細書に記載さ れているのと同様にその内容が本明細書に対する参考として援用されるべきであるこ とが理解される。  [0054] As described above, the power of the present invention exemplified by the preferred embodiment of the present invention. The present invention should not be construed as being limited to this embodiment. It is understood that the scope of the present invention should be construed only by the claims. It is understood that those skilled in the art can implement an equivalent range based on the description of the present invention and the common general technical knowledge from the description of specific preferred embodiments of the present invention. Patents, patent applications, and literature references cited in this specification should be incorporated by reference as if the contents themselves were specifically described in the present specification. Is understood.
実施例  Example
[0055] (実施例 1) [Example 1]
予めァスファルタイトの 1種であるギルソナイトを 35重量部に対し、有機溶媒として口 ーズマリー油 65重量部を加え、 120°Cで 1時間加熱、撹拌して濾過処理した後、蒸 発した分量に見合う量のローズマリー油を補充して、ギルソナイト 35%の溶解液を作 製し、これを有機ビヒクルとする。次に炭酸銀 (銀濃度： 79. 6重量％) 18重量部に対 し、有機溶媒としてテルビネオール 11. 5重量部を加え、プロペラ式撹拌機で攪拌後 、前記ギルソナイト 35%溶解液 (有機ビヒクル)を 10重量部と有機酸銀としてォレイン 酸銀 (銀濃度： 27. 7重量％)を 6重量部添加し、 150°Cで 70分間加熱、撹拌して架 橋反応させ、冷却して得たペースト状の組成物に Rh金属有機物 (Rh濃度： 1重量％ )を 1重量部、 Pd金属有機物（Pd濃度： 20重量％)を 1重量部、さらに基板への密着 性向上のため、 Bi金属有機物（Bi濃度： 3重量％)を 1. 5重量部添加後、三本ロール により分散均等化した後、粘度を調整するために必要に応じて所要量のテルビネオ ールを加えて、銀ペースト組成物を 50重量部得る。ここで得られた、銀ペースト組成 物の銀濃度は、約 32重量％で、 Pd濃度は約 0. 4重量％、 Rh濃度は約 0. 01重量 %、 Bi濃度は 0. 045重量0 /0である。こうして得られた銀ペースト組成物をステンレス 3 25メッシュ、乳剤厚み 10 μ mでガラス基板に印刷したところ、パターン幅 80 μ m、ス ペース 50 μ πιの高精細な電極パターンの印刷ができた。これは、ォレイン酸とァスフ アルタイトの一種であるギルソナイトとが化学架橋し、にじみにくいペースト組成になつ たことが原因と推定される。 Add 65 parts by weight of oral mary oil as an organic solvent to 35 parts by weight of Gilsonite, a kind of asphaltite, and heat and agitate for 1 hour at 120 ° C. Of rosemary oil to make a 35% solution of Gilsonite, which is used as the organic vehicle. Next, 11.5 parts by weight of tervineol as an organic solvent is added to 18 parts by weight of silver carbonate (silver concentration: 79.6% by weight), and after stirring with a propeller type stirrer, the 35% solution of Gilsonite (organic vehicle) is added. ) And 10 parts by weight of organic oleate and 6 parts by weight of silver oleate (silver concentration: 27.7% by weight), heated and stirred at 150 ° C for 70 minutes to cause a bridge reaction and cooled. 1 part by weight of Rh metal organic substance (Rh concentration: 1% by weight), 1 part by weight of Pd metal organic substance (Pd concentration: 20% by weight), and Bi to improve the adhesion to the substrate. Three rolls after adding 1.5 parts by weight of organic metal (Bi concentration: 3% by weight) After dispersing and equalizing by the above, a necessary amount of tervineol is added as necessary to adjust the viscosity to obtain 50 parts by weight of a silver paste composition. Obtained here, the silver concentration of the silver paste composition is about 32 wt%, Pd concentration of about 0.4 wt%, Rh concentration of about 0.01 wt%, Bi concentration 0.045 Weight 0 / 0 . When the silver paste composition thus obtained was printed on a glass substrate with a stainless steel 325 mesh and an emulsion thickness of 10 μm, a high-definition electrode pattern with a pattern width of 80 μm and a space of 50 μπι could be printed. This is presumably because oleic acid and gyrsonite, a type of asphaltite, chemically cross-linked, resulting in a paste composition that does not bleed easily.
[0056] 乾燥後の膜厚は、 8 μ mであった。次にこの乾燥膜を 550°C焼成したところ、 1. 2 mの銀薄膜が得られた。この電極膜のシート抵抗値は、 25πιΩであった。ここで得ら れた銀薄膜電極にスコッチテープを用いて剥離試験を実施した力 全く剥離すること はなかった。さらに耐熱試験として、 600°Cで、 5回焼成を繰り返した力 抵抗値の変 化率は 5%以下であり、測定誤差範囲であった。  [0056] The film thickness after drying was 8 µm. Next, when this dried film was baked at 550 ° C, a 1.2 m silver thin film was obtained. The sheet resistance value of this electrode film was 25πιΩ. The force of the peel test using a scotch tape on the silver thin film electrode obtained here did not peel at all. Furthermore, as a heat resistance test, the rate of change in the force resistance value after repeated baking at 600 ° C for 5 times was 5% or less, which was within the measurement error range.
[0057] 同様の銀ペースト製造方法で表 1に示す各種組成にっレ、てガラス基板への銀薄膜 電極形成後、電気的評価を実施した。  [0057] Electrical evaluation was carried out after forming a silver thin film electrode on a glass substrate according to various compositions shown in Table 1 by the same silver paste production method.
[0058] [表 1]  [0058] [Table 1]
Figure imgf000013_0001
Figure imgf000013_0001
実施例 1— 1、 1一 2、 1一 5より、 Bi金属有機物や Si金属有機物、 Cr金属有機物の 添加により、ガラス基板への密着性の向上が理解できる。同様に、焼成ドリフトの安定 性にっレ、ては、 Rhおよび Pdの金属有機物が有効であることが理解できる。  From Examples 1-1, 1 1 2 and 1 1 5 it can be seen that the addition of Bi metal organics, Si metal organics and Cr metal organics improves the adhesion to the glass substrate. Similarly, it can be understood that Rh and Pd metal organics are effective for the stability of firing drift.
[0059] また、実施例 1一 4より、銀濃度が 25重量％程度の銀電極薄膜は、耐熱安定性に 劣ることが理解できる。  [0059] From Examples 1 to 4, it can be understood that the silver electrode thin film having a silver concentration of about 25% by weight is inferior in heat resistance stability.
[0060] 更に同様の試験を 96%アルミナ基板に対し実施した。この場合、チップ抵抗器等 の電子部品用途を想定し、 850°C焼成で銀電極薄膜の評価を行った (表 2)。  [0060] Further, a similar test was performed on a 96% alumina substrate. In this case, the silver electrode thin film was evaluated by firing at 850 ° C, assuming the use of electronic components such as chip resistors (Table 2).
[0061] [表 2] [0061] [Table 2]
差替え用紙 （¾¾IIJ26) 銀 S度 Rh 度 Pd漠度 Bほ度 S 度 Cr漠度 焼成 シー卜 耐熟性 Replacement paper (¾¾IIJ26) Silver S degree Rh degree Pd Vagueness B Moderate S degree Cr
温度 &杭旗 850¾ x 5密》性 実施例 1 -β 32% 0.004% 0.2QH 0.045% 一 ― 850°C eOmo m く 15% 良好 実施 «卜 7 32% 0.005% 0.20% ― 一 ― 850°C 72mohm <20 議 突施例 1 -8 32% ― 一 0.045% ― ― 850。C OPEN OPEN 良好 実施例 1 -9 25X 0.002» 0.20% 0.045% ― ― 850°C 125mohm <30¾ 良好 実拖例 1 -10 40% 0.010% 2.00% 一 0.05% 0.02% 85Q¾ 58mohm <5% 良好 実施例 1—6〜； LOにおいても、実施例 1一:!〜 5同様、 Rh、 Pd金属有機物の添カロ による耐熱安定性と Bi、 Si、 Cr金属有機物添カ卩によるアルミナ基板への密着性向上 を読み取ることができる。  Temperature & pile flag 850¾ x 5 dense Example 1 -β 32% 0.004% 0.2QH 0.045% One ― 850 ° C eOmo m 15% Good Implementation «卜 7 32% 0.005% 0.20% ― One ― 850 ° C 72mohm <20 Proposed cases 1 -8 32% ― 1 0.045% ― ― 850. C OPEN OPEN Good Example 1 -9 25X 0.002 »0.20% 0.045% ― ― 850 ° C 125mohm <30¾ Good practice 1 -10 40% 0.010% 2.00% One 0.05% 0.02% 85Q¾ 58mohm <5% Good Example 1-6 ~; also in LO, as in Example 1-1:! ~ 5, heat resistance stability due to addition of Rh, Pd metal organics and improved adhesion to alumina substrate by addition of Bi, Si, Cr metal organics Can be read.
[0062] 以上の実施例では、耐熱性を向上させる材料として Rhおよび Pdの金属有機物の 効果を例示したが、白金および Ruの金属有機物を用いた場合でも、その効果は同 様である。また、基板への密着性を確保するための材料として、 Bi、 Si、 Crの金属有 機物による効果を例示した力 Bや Pbの金属有機物を添加した場合も、同様の効果 を得ることができることは言うまでもなレ、。  In the above examples, the effects of the Rh and Pd metal organic substances are exemplified as the material for improving the heat resistance, but the effects are the same even when the platinum and Ru metal organic substances are used. The same effect can also be obtained by adding force B or Pb metal organics that illustrate the effects of Bi, Si, Cr metal organic materials as materials to ensure adhesion to the substrate. Needless to say, you can do it.
[0063] 更に、 Pdの金属有機物を意図的に多く添加する（たとえば、 Pd量を銀の含有量の 5重量％以上添加させる）ことで、マイグレーションの抑制効果を得ることも可能である  [0063] Furthermore, it is also possible to obtain an effect of suppressing migration by intentionally adding a large amount of metal organic matter of Pd (for example, adding 5% by weight or more of Pd content to the silver content).
[0064] (実施例 2) [0064] (Example 2)
次に本発明における他の銀ペースト組成物につ!、て説明する。  Next, another silver paste composition in the present invention will be described.
[0065] 無機酸銀として炭酸銀 (銀濃度： 79. 8重量％) 50重量部を用いた。 [0065] As inorganic silver, 50 parts by weight of silver carbonate (silver concentration: 79.8% by weight) was used.
[0066] 炭酸銀は粉末状の物質であるが、粉が凝集した塊が点在するため、予め混合粉砕 機で、予備混合し、凝集粉を解砕したのち、有機ビヒクルとしてテルペン類のアビェ チン酸をローズマリ一油を 2： 1の混合比で溶解して得られるァビエチン酸ビークルを 5重量部、ェチルセルロースとして、エトセル 25cpsとテルビネオールを 1 : 9で混合溶 解したェチルセルロースビークルを 30重量部、焼結抑制剤として Rhの金属有機物（ Rh濃度: 5重量％)を 1. 1重量部、ガラス成分としてォクチル酸鉛 (Pb濃度：20重量 %)を 1. 4重量部、ォクチル酸銅 (Cu濃度：5重量％)を 1 · 3重量部、ホウ素レジネー ト（B濃度： 2. 16重量％)を 0. 6重量部、珪素べンジルアルコレート（Si濃度： 9. 36 重量。 /。）を 0. 35重量部添加した。これらをすベて配合したのち、 150度で、 50分攪 [0066] Although silver carbonate is a powdery substance, there are scattered lumps of agglomerated powder. Premixing is performed beforehand with a mixing and grinding machine, and the agglomerated powder is crushed, and then the terpene compound is used as an organic vehicle. A cetylcellulose vehicle in which 5 parts by weight of abietic acid vehicle obtained by dissolving rose marinic oil in a 2: 1 mixing ratio with ethylcellulose and ethcel cellulose 25cps and tervineol in a 1: 9 mixture was dissolved. 30 parts by weight, 1.1 parts by weight of Rh metal organic matter (Rh concentration: 5% by weight) as a sintering inhibitor, 1.4 parts by weight of lead octylate (Pb concentration: 20% by weight) as a glass component, octyl 1.3 parts by weight of copper oxide (Cu concentration: 5% by weight), 0.6 parts by weight of boron resinate (B concentration: 2.16% by weight), silicon benzyl alcoholate (Si concentration: 9.36) Weight) was added in an amount of 0.35 parts by weight. After all these ingredients are mixed, they are stirred at 150 degrees for 50 minutes.
差替え用紙 （aiij26) Replacement paper (aiij26)
拌機で攪拌した。冷却後、粘度調整用の溶剤として、タービネオルを添カ卩し、ペース Stir with a stirrer. After cooling, add turbineol as a solvent for viscosity adjustment,
差替え用鉞 トの粘度を調整した。 325ステンレスメッシュ、乳剤厚み 10ミクロンのスクリーンにてガ ラス基板 (旭硝子製 PD200)上に印刷し、 120°Cで 10分間乾燥させたのちの乾燥膜 厚は、 9ミクロンであった。更に、 600°C、キープ 10分で焼成したところ約 2. 5ミクロン の銀薄膜が得られた。シート抵抗値は、約 22πι Ω (比抵抗:約 4. 4 μ Ω ' cm)であつ た。本ペーストは銀濃度が約 40重量％であるため、比較的厚い膜が得られたと考え られる。本実施例では、エトセルとテルペン類の樹脂の混合物を用いたが、粘度の要 求を満たせば、単独で用いても良い。同様にアクリル榭脂も同様に使用することがで きる。またクロスカット法による密着性も何ら問題なぐ全く剥離は観察されな力つた。 これは、鉛、ホウ素、珪素の金属有機物の焼成によるガラス化と銅の金属有機物が焼 成仮定で酸化銅となり、酸化銅による化学的結合も寄与したと推定される。一般に酸 ィ匕銅による密着性は、アルミナ基板との反応において活用されるのは、周知の事実 であるが、実際本実施例の銀ペースト組成物をアルミナ基板に形成した場合も、同様 に密着性は良好であった。 Replacement bowl The viscosity of the toner was adjusted. After printing on a glass substrate (PD200 manufactured by Asahi Glass) with a screen of 325 stainless steel mesh and emulsion thickness of 10 microns, the film thickness after drying at 120 ° C for 10 minutes was 9 microns. When fired at 600 ° C for 10 minutes, a silver thin film of about 2.5 microns was obtained. The sheet resistance was about 22πι Ω (specific resistance: about 4.4 μΩ 'cm). Since this paste has a silver concentration of about 40% by weight, it is considered that a relatively thick film was obtained. In this example, a mixture of ethosel and terpene resins was used, but it may be used alone if the viscosity requirement is satisfied. Similarly, acrylic resin can be used as well. Moreover, no peeling was observed without any problem in the adhesion by the cross-cut method. This is presumed that the vitrification of metal organics such as lead, boron, and silicon and the metal organics of copper became copper oxide on the assumption of firing, and the chemical bonding by copper oxide also contributed. In general, it is a well-known fact that the adhesion by acid-copper is utilized in the reaction with the alumina substrate. However, when the silver paste composition of this example is actually formed on the alumina substrate, the adhesion is also the same. The property was good.
[0067] このように、ガラス成分となる材料を適宜選択することで、本発明により得られるぺー スト組成物が形成される基板との密着性を十分得られることになる。  [0067] As described above, by appropriately selecting the material to be the glass component, sufficient adhesion to the substrate on which the paste composition obtained by the present invention is formed can be obtained.
[0068] し力しながら、本発明による銀ペースト組成物を約 23°C程度の室温で、 1週間放置 後、同様に印刷〜焼成を実施したところ、ペーストがやや硬くなるとともに、印刷後の 膜表面および、焼成後の膜表面に、混練直後のものに比較し凹凸がみられた。表面 粗さは、混練直後のもの力 Rzが約 0. 2 mであったのに対し、 1週間後のものが、 Rzが約 0. となった。これは、ペースト中の炭酸銀が再凝集を起こしたためと推 定される。ステアリン酸、ォレイン酸等の脂肪酸の添カ卩により、炭酸銀の再凝集を抑 制させることも可能であった。  [0068] The silver paste composition according to the present invention was left to stand at room temperature of about 23 ° C for 1 week, and then printed and baked in the same manner. Concavities and convexities were observed on the film surface and the film surface after firing as compared with that immediately after kneading. As for the surface roughness, the force Rz immediately after kneading was about 0.2 m, whereas the one after one week had Rz of about 0.2. This is presumed to be due to reagglomeration of silver carbonate in the paste. By adding fatty acids such as stearic acid and oleic acid, reaggregation of silver carbonate could be suppressed.
[0069] (実施例 3)  [0069] (Example 3)
次に実施例 2の改善を目指し、実施例における炭酸銀の 1重量部をォレイン酸銀に 置換した銀ペースト組成物について説明する。  Next, with the aim of improving Example 2, a silver paste composition in which 1 part by weight of silver carbonate in Example is replaced with silver oleate will be described.
[0070] 無機酸銀としての炭酸銀 (銀濃度： 79. 8重量％)を 50重量部から 44重量部に減ら し、有機酸銀としてォレイン酸銀 (銀濃度： 27. 7重量％) 18重量部を添加した。（焼 成後の銀濃度は、実施例 2同様、約 40重量％となる。 ) 炭酸銀もォレイン酸銀も粉末なので、予め混合粉砕機で、予備混合し、凝集粉を解 砕したのち、実施例 2と同様に有機ビヒクルとしてテルペン類のアビェチン酸を口 ·一 ズマリー油を 2 : 1の混合比で溶解して得られるァビエチン酸ビークルを 5重量部、ェ チルセルロースとして、エトセル 25cpsとテルビネオールを 1： 9で混合溶解したェチ ルセルロースビークルを 30重量部、焼結抑制剤として Rhの金属有機物 (Rh濃度： 5 重量％)を 1. 1重量部、ガラス成分としてォクチル酸鉛 (Pb濃度： 20重量％)を 1. 4 重量部、ォクチル酸鋼 (Cu濃度： 5重量％)を 1. 3重量部、ホウ素レジネート（B濃度： 2. 16重量％)を 0. 6重量部、珪素べンジルアルコレート（Si濃度： 9. 36重量％)を 0 . 35重量部添加した。これらをすベて配合したのち、 150度で、 50分撹拌機で撹拌 した。冷却後、粘度調整用の溶剤として、タービネオルを添加し、ペーストの粘度を 調整した。 325ステンレスメッシュ、乳剤厚み 10ミクロンのスクリーンにてガラス基板（ 旭硝子製 PD200)上に印刷し、 120°Cで 10分間乾燥させたのちの乾燥膜厚は、 8. 5ミクロンであった。更に、 600°C、キープ 10分で焼成したところ約 2. 5ミクロンの銀薄 膜が得られた。シート抵抗値は、約 20πι Ω (比抵抗:約 4 Ω 'cm)であった。これら の特性は実質的に実施例 2とほぼ同特性であるということができる。その他、密着性 等についても、実施例 2と同様であった。本ペースト組成物を約 23°Cで 1週間放置後 、印刷および焼成を行った力 本ペーストについては、混練直後と 1週間放置後の表 面粗さに特に有意な差は観察されな力つた。ォレイン酸銀が、銀ペースト組成物の分 散性の安定ィヒに寄与したものと推定される。同様の効果は、酢酸銀、乳酸銀、ドデシ ルメルカブタン銀等の有機酸銀に共通して観察されるが、有機酸を構成する分子量 の大き!/ヽォレイン酸銀が分散安定性に最も優れる。 [0070] Silver carbonate (silver concentration: 79.8% by weight) as inorganic acid silver was reduced from 50 parts by weight to 44 parts by weight, and organic oleate (silver concentration: 27.7% by weight) 18 Part by weight was added. (The silver concentration after calcination is about 40% by weight as in Example 2.) Since both silver carbonate and silver oleate are powders, they are premixed in advance with a mixing grinder to break up the agglomerated powder, and then terpene abietic acid is used as an organic vehicle in the same manner as in Example 2. : 5 parts by weight of an abietic acid vehicle obtained by dissolving at a mixing ratio of 1: 30 parts by weight of an ethyl cellulose vehicle in which ethyl cellulose is mixed and dissolved at a ratio of 1: 9 as ethyl cellulose, and 30 parts by weight of a sintering inhibitor As Rh metal organic matter (Rh concentration: 5 wt%) 1.1 parts by weight, lead octylate (Pb concentration: 20 wt%) as glass components, 1.4 parts by weight, octylate steel (Cu concentration: 5 wt%) %) 1.3 parts by weight, boron resinate (B concentration: 2.16% by weight) 0.6 parts by weight, silicon benzyl alcoholate (Si concentration: 9.36% by weight) 0.35 parts by weight Added. After all of these were blended, the mixture was stirred with a stirrer at 150 degrees for 50 minutes. After cooling, turbineol was added as a viscosity adjusting solvent to adjust the viscosity of the paste. After printing on a glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) with a screen of 325 stainless mesh and emulsion thickness of 10 microns, the film thickness after drying at 120 ° C for 10 minutes was 8.5 microns. When fired at 600 ° C for 10 minutes, a silver thin film of about 2.5 microns was obtained. The sheet resistance value was about 20πι Ω (specific resistance: about 4 Ω′cm). It can be said that these characteristics are substantially the same as those of Example 2. In addition, the adhesion and the like were the same as in Example 2. The strength of the paste composition after printing and baking after being left at about 23 ° C for 1 week. For this paste, no significant difference was observed in the surface roughness immediately after kneading and after standing for 1 week. . It is estimated that silver oleate contributed to the dispersion stability of the silver paste composition. The same effect is observed in common with organic acid silver such as silver acetate, silver lactate, silver dodecyl mercaptan, etc., but the molecular weight constituting the organic acid! / Silver oleate is most excellent in dispersion stability.
[0071] (実施例 4)  [Example 4]
本発明の他の実施例における銀ペースト組成物について説明する。  The silver paste composition in the other Example of this invention is demonstrated.
[0072] 無機酸銀として炭酸銀 (銀濃度：79. 8重量％)を 20. 4重量部と、有機酸銀として ォレイン酸銀 (銀濃度: 27. 7重量％)を 7. 1重量部を添加後、混合粉砕機で、予備 混合し、凝集粉を解砕したのち、有機ビヒクルとしてテルペン類のアビェチン酸をロー ズマリー油を 2 : 1の混合比で溶解して得られるァビエチン酸ビークルを 3重量部、口 ーズマリー油で溶解したギルナライト 35%溶解液を 13重量部、焼結抑制剤として Rh の金属有機物 (Rh濃度： 5重量％)を 1. 5重量部と Pdの金属有機物（Pd濃度： 9. 55 重量％)を 2. 1重量部、ガラス成分としてビスマスレジネート（Bi濃度： 3. 00重量％) を 1. 5重量部添加した。これらをすベて配合したのち、 150度で、 30分攪拌機でカロ 熱攪拌した。冷却後、粘度調整用の溶剤として、タービネオルを約 11重量部添加し 、ペーストの粘度を調整した。 325ステンレスメッシュ、乳剤厚み 10ミクロンのスクリー ンにてガラス基板 (旭硝子製 PD200)上に印刷し、ファインパターン印刷性を確認し た。パターン幅 Zスペースは 75ミクロンまで印刷することができた力 それよりスぺー スがせまいところは、 -ジミにより部分的に、線がつながった。本ペーストの粘度特性 は、ブルックフィールド回転粘度計 1回転で 420pa' s、 10回転で 80. 8pa' sであり、 回転粘度比（1回転の粘度 Z10回転の粘度）は、約 5であった。本ペーストの作成時 、ペーストを 150°Cで 30分加熱撹絆した力 加熱撹拌時間を 60分以上行うと、架橋 反応が起こり粘度特性が変化する。丁度加熱攪拌を 150°C、 60分行ったものの粘度 特性はブルックフィールド回転粘度計 1回転で 2240pa' s、 10回転で 188pa' sであり 、回転粘度比（1回転の粘度 Z10回転の粘度）は、約 12となり、非常にチクソトロピー 性の高いペーストとなる。この粘度特性のペーストを 325ステンレスメッシュ、乳剤厚 み 10ミクロンのスクリーンにてガラス基板 (旭硝子製 PD200)上に印刷し、ファインパ ターン印刷性を確認するとパターン幅 Zスペースは 40ミクロンまで印刷することがで きた。 [0072] 20.4 parts by weight of silver carbonate (silver concentration: 79.8% by weight) as inorganic acid silver and 7.1 parts by weight of silver oleate (silver concentration: 27.7% by weight) as organic acid silver After mixing, pre-mix in a mixing pulverizer, crush the agglomerated powder, and then use the avipenic acid vehicle obtained by dissolving the terpene abietic acid as the organic vehicle in a 2: 1 mixing ratio. 3 parts by weight, 13 parts by weight of 35% solution of girnarite dissolved in mouthmary oil, Rh as sintering inhibitor 1.5 parts by weight of metal organics (Rh concentration: 5% by weight) and 2.1 parts by weight of metal organics (Pd concentration: 9.55% by weight) of Pd, bismuth resinate (Bi concentration: 3. 00 parts by weight) was added at 1.5 parts by weight. After all of these were blended, the mixture was stirred for 150 minutes at 150 degrees with a stirrer. After cooling, about 11 parts by weight of terbinol was added as a viscosity adjusting solvent to adjust the viscosity of the paste. A fine pattern printability was confirmed by printing on a glass substrate (PD200 manufactured by Asahi Glass) with a screen of 325 stainless mesh and emulsion thickness of 10 microns. Pattern width Z space is the force that can print up to 75 microns. Where space is narrower than that, -Jimi partially connected the lines. The viscosity characteristics of this paste were 420 pa's at one revolution of Brookfield rotary viscometer, 80.8 pa's at 10 revolutions, and the rotational viscosity ratio (viscosity of one revolution Z10 revolutions) was about 5. . At the time of making this paste, if the paste is heated and stirred at 150 ° C for 30 minutes If the heating and stirring time is 60 minutes or longer, a crosslinking reaction occurs and the viscosity characteristics change. Viscosity characteristics of exactly what was heated and stirred at 150 ° C for 60 minutes is 2240 pa's for one revolution of Brookfield rotary viscometer, 188 pa's for 10 revolutions, and the rotational viscosity ratio (viscosity for one revolution Z10 viscosity for one revolution) Becomes about 12 and becomes a very thixotropic paste. A paste with this viscosity characteristic is printed on a glass substrate (PD200 made by Asahi Glass) using a screen of 325 stainless mesh and emulsion thickness of 10 microns, and if the fine pattern printability is confirmed, the pattern width Z space can be printed up to 40 microns. did it.
[0073] このように、ァビエチン酸やギルソナイトを含有するペーストは、ペーストの過熱攪拌 条件次第で、架橋反応により粘度特性を容易に変化させることができるという優れた 特性を有する。  [0073] As described above, the paste containing abietic acid or gilsonite has an excellent characteristic that the viscosity characteristic can be easily changed by a crosslinking reaction depending on the superheated stirring condition of the paste.
[0074] ところで、本ペーストの印刷パターンを 120°Cで 10分間乾燥させたのちの乾燥膜厚 は、 8ミクロンであった。更に、 600°C、キープ 10分で焼成したところ約 1ミクロンの銀 薄膜が得られた。シート抵抗値は、約 35πι Ω (比抵抗約 4 Ω 'cm)であった。  [0074] Incidentally, after the printed pattern of this paste was dried at 120 ° C for 10 minutes, the dry film thickness was 8 microns. Furthermore, when fired at 600 ° C for 10 minutes, a silver thin film of about 1 micron was obtained. The sheet resistance value was about 35πι Ω (specific resistance about 4 Ω′cm).
[0075] (実施例 5)  [0075] (Example 5)
本発明の他の実施例における銀ペースト組成物について説明する。  The silver paste composition in the other Example of this invention is demonstrated.
[0076] 無機酸銀として酸化銀 (銀濃度 : 87. 1重量％)を 18. 7重量部と、有機酸銀として ォレイン酸銀 (銀濃度: 27. 7重量％)を 7. 1重量部を添加後、混合粉砕機で、予備 混合し、凝集粉を解砕したのち、有機ビヒクルとしてテルペン類のアビェチン酸をロー ズマリー油を 2 : 1の混合比で溶解して得られるァビエチン酸ビークルを 3重量部、口 ーズマリー油で溶解したギルソライト 35%溶解液を 13重量部、焼結抑制剤として Rh の金属有機物 (Rh濃度： 5重量％)を 1. 5重量部と Pdの金属有機物（Pd濃度： 9. 55 重量％)を 2. 1重量部、ガラス成分としてビスマスレジネート（Bi濃度： 3. 00重量％) を 1. 5重量部添加した。これらをすベて配合したのち、 150度で、 30分攪拌機でカロ 熱攪拌した。冷却後、粘度調整用の溶剤として、タービネオルを約 11重量部添加し 、ペーストの粘度を調整した。 400ステンレスメッシュ、乳剤厚み 8ミクロンのスクリーン にてガラス基板 (旭硝子製 PD200)上に印刷し、 120°Cで 10分間乾燥させたのちの 乾燥膜厚は、 6ミクロンであった。 [0076] 18.7 parts by weight of silver oxide (silver concentration: 87.1% by weight) as inorganic acid silver and 7.1 parts by weight of silver oleate (silver concentration: 27.7% by weight) as organic acid silver After adding After mixing and crushing the agglomerated powder, 3 parts by weight of an abietic acid vehicle obtained by dissolving a terpene abietic acid in a 2: 1 mixture ratio as an organic vehicle and dissolved in mouthmary oil 13 parts by weight of Gilsolite 35% solution, 1.5 parts by weight of Rh metal organics (Rh concentration: 5% by weight) and 2 parts of Pd metal organics (Pd concentration: 9.55% by weight) as sintering inhibitors 1 part by weight, 1.5 parts by weight of bismuth resinate (Bi concentration: 3.00% by weight) was added as a glass component. After all of these were blended, the mixture was stirred for 150 minutes at 150 degrees with a stirrer. After cooling, about 11 parts by weight of terbinol was added as a viscosity adjusting solvent to adjust the viscosity of the paste. After printing on a glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) with a 400 stainless mesh, 8 micron emulsion screen, and drying at 120 ° C for 10 minutes, the dry film thickness was 6 microns.
[0077] 更に、 600°C、キープ 10分で焼成したところ約 0. 7ミクロンの銀薄膜が得られた。シ ート抵抗値は、約 55πι Ω (比抵抗:約 3、 9 μ Ω ' cm)であった。  [0077] Further, when baked at 600 ° C for 10 minutes, a silver thin film of about 0.7 microns was obtained. The sheet resistance was about 55πι Ω (specific resistance: about 3, 9 μΩ 'cm).
[0078] また密着性にっ ヽても全く問題なかった。  [0078] Further, there was no problem even if the adhesion was improved.
[0079] 本実施例に示すように無機酸銀が酸ィ匕銀であっても、別段問題がないことが理解 できる。  [0079] It can be understood that there is no particular problem even if the inorganic acid silver is acid silver as shown in this example.
[0080] (比較例 1)  [0080] (Comparative Example 1)
有機酸銀としてォレイン酸銀 (銀濃度： 27. 7重量0 /0)を 15重量部、有機ビヒクルとし てローズマリー油で溶解したギルソライト 35%溶解液を 7. 5重量部、焼結抑制剤とし て Rhの金属有機物 (Rh濃度： 5重量％)を 0. 45重量部と Pdの金属有機物（Pd濃度 : 9. 55重量0 /0)を 1. 46重量部、ガラス成分としてビスマスレジネート（Bi濃度： 3. 00 重量％)を 1重量部添加した。これらをすベて配合したのち、 150度で、 30分攪拌機 で加熱攪拌した。冷却後、粘度調整用の溶剤として、タービネオルを約 3重量部添カロ し、ペーストの粘度を調整した。本銀ペースト組成物を 325ステンレスメッシュ、乳剤 厚み 10ミクロンのスクリーンにてガラス基板 (旭硝子製 PD200)上に印刷し、 120°C で 10分間乾燥させたのちの乾燥膜厚は、 8ミクロンであった。更に、 600°C、キープ 1 0分で焼成したところ約 0. 4ミクロンの銀薄膜が得られた。シート抵抗値は、約 420m Ω (比抵抗:約 17 Ω ' cm)と非常に抵抗値の大きい膜となった。 Orein silver as the organic acid silver (silver concentration: 27.7 wt 0/0) 15 parts by weight, 7.5 parts by weight of Girusoraito 35% solution dissolved in rosemary oil and an organic vehicle, sintering inhibitors and to Rh metal organic: metal organic substances (Rh concentration: 5 wt%) of 0.45 parts by weight of Pd (Pd concentration: 9. 55 weight 0/0) 1. 46 wt parts, bismuth resinate as the glass component ( 1 part by weight of Bi concentration: 3.00% by weight) was added. After all of these were blended, they were heated and stirred with a stirrer at 150 degrees for 30 minutes. After cooling, the viscosity of the paste was adjusted by adding about 3 parts by weight of terneol as a solvent for adjusting the viscosity. This silver paste composition was printed on a glass substrate (PD200 manufactured by Asahi Glass) using a 325 stainless steel mesh, 10-micron emulsion screen, and dried at 120 ° C for 10 minutes, resulting in a dry film thickness of 8 microns. It was. Further, when fired at 600 ° C. for 10 minutes, a silver thin film of about 0.4 microns was obtained. The sheet resistance value was about 420 mΩ (specific resistance: about 17 Ω ′ cm), and the film had a very high resistance value.
[0081] 本焼成膜を 600°Cで再焼成を行ったところ、 2回目で断線状態となった。 これは、本比較例における銀ペースト組成物の銀濃度が約 17重量％と低いことが原 因で、焼成による膜の焼結促進により、膜が島状に分離し、やがて断線状態に至つ たと考えられる。 [0081] When the fired film was refired at 600 ° C, it was disconnected in the second time. This is because the silver concentration of the silver paste composition in this comparative example is as low as about 17% by weight, and the film is separated into islands by accelerating the sintering of the film by firing, and eventually the disconnection state is reached. It is thought.
産業上の利用可能性 Industrial applicability
以上のように本発明によれば、各種電子部品の配線電極および端子電極の薄膜 化を高精度かつ安価に形成することができ、電子部品の小型高精度化に寄与するも のである。また、 PDPに代表されるフラットディスプレイパネル等の前面板と言われる 表示部のバスラインの電極の薄膜ィ匕が求められる中、本発明によるファインパターン 印刷により、薄膜の信頼性を向上させる電極としても活用でき、産業上きわめて有用 な発明である。  As described above, according to the present invention, thinning of wiring electrodes and terminal electrodes of various electronic components can be formed with high accuracy and at low cost, which contributes to miniaturization and high accuracy of electronic components. In addition, a thin film layer of a bus line electrode of a display portion called a front panel of a flat display panel or the like typified by a PDP is required. As an electrode for improving thin film reliability by fine pattern printing according to the present invention. This is an industrially very useful invention.

Claims

請求の範囲 The scope of the claims
[I] 以下の成分：  [I] The following ingredients:
A)無機酸銀および,または有機酸銀；  A) inorganic acid silver and / or organic acid silver;
B)有機バインダ;ならびに  B) organic binders; and
C)溶剤、  C) solvent,
を含有する銀ペースト組成物であって、  A silver paste composition comprising:
該成分 A)に基づく銀の含有量が、該組成物の全重量を基準として 10〜50重量％ である、銀ペースト組成物。  A silver paste composition, wherein the silver content based on component A) is from 10 to 50% by weight, based on the total weight of the composition.
[2] 銀粉末を実質的に含有しない、請求項 1に記載の銀ペースト組成物。 [2] The silver paste composition according to claim 1, which contains substantially no silver powder.
[3] 前記無機酸銀は、酸ィ匕銀または炭酸銀である、請求項 1に記載の銀ペースト組成物 [3] The silver paste composition according to claim 1, wherein the inorganic acid silver is acid silver or silver carbonate.
[4] 前記有機酸銀は、酢酸銀、乳酸銀、ォレイン酸銀または安息香酸銀である、請求項[4] The organic acid silver is silver acetate, silver lactate, silver oleate or silver benzoate.
1に記載の銀ペースト組成物。 The silver paste composition according to 1.
[5] 前記成分 A)は、無機酸銀と有機酸銀との混合物である、請求項 1に記載の銀ペース ト組成物。 [5] The silver paste composition according to claim 1, wherein the component A) is a mixture of inorganic acid silver and organic acid silver.
[6] 前記有機バインダは、ァスファルタイトである、請求項 1に記載の銀ペースト組成物。  6. The silver paste composition according to claim 1, wherein the organic binder is asphaltite.
[7] 前記有機バインダは、アルカリ可溶性榭脂、光硬化性モノマーおよび光重合開始剤 を含有する、請求項 1に記載の銀ペースト組成物。 7. The silver paste composition according to claim 1, wherein the organic binder contains an alkali-soluble resin, a photocurable monomer, and a photopolymerization initiator.
[8] 追加の成分として、ロジウム、ノラジウム、白金およびルテニウム力もなる群力も選択 される少なくとも一種以上の金属の金属有機化合物または金属有機スルホレジネー トをさらに含有する、請求項 1に記載の銀ペースト組成物。 [8] The silver paste composition according to claim 1, further comprising, as an additional component, at least one metal metal organic compound or metal organic sulforesinate that also has a group power including rhodium, noradium, platinum, and ruthenium power. object.
[9] 請求項 1に記載の銀ペースト組成物力 得られる厚み 0. 2〜2. 5 μ mの銀薄膜。 [9] The silver paste composition according to claim 1, wherein the obtained silver thin film has a thickness of 0.2 to 2.5 μm.
[10] 請求項 9に記載の銀薄膜を含む、電子部品用薄膜導体。 [10] A thin film conductor for electronic parts, comprising the silver thin film according to claim 9.
[II] 請求項 9に記載の銀薄膜を含む、ディスプレイデバイス用配線材料。  [II] A wiring material for a display device, comprising the silver thin film according to claim 9.
[12] 以下の工程： [12] The following steps:
a)無機酸銀および Zまたは有機酸銀と有機ノ インダと溶剤とを含有する銀ペースト 組成物の膜を基板上に形成する工程；  a) a step of forming a film of a silver paste composition containing inorganic acid silver and Z or organic acid silver, an organic indicator and a solvent on a substrate;
b)該膜を乾燥する工程；および c)該乾燥膜を焼成する工程、 b) drying the membrane; and c) firing the dry film,
を包含する、銀薄膜の製造方法。  A method for producing a silver thin film.
[13] 前記工程 a)は、スクリーン印刷によって行われる、請求項 12に記載の方法。  13. The method according to claim 12, wherein the step a) is performed by screen printing.
[14] 前記工程 b)は、 90〜150°Cで行われる、請求項 12に記載の方法。 [14] The method according to claim 12, wherein the step b) is performed at 90 to 150 ° C.
[15] 前記工程 c)は、 450〜700°Cで行われる、請求項 12に記載の方法。 [15] The method according to claim 12, wherein the step c) is performed at 450 to 700 ° C.
[16] 請求項 12に記載の方法によって得られる、厚み 0. 2〜2. 5 μ mの銀薄膜。 [16] A silver thin film having a thickness of 0.2 to 2.5 μm obtained by the method according to claim 12.
PCT/JP2005/018030 2004-09-29 2005-09-29 Silver paste composition WO2006035908A1 (en)

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WO2015064567A1 (en) 2013-10-31 2015-05-07 昭和電工株式会社 Electrically conductive composition for thin film printing, and method for forming thin film conductive pattern
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WO2015064567A1 (en) 2013-10-31 2015-05-07 昭和電工株式会社 Electrically conductive composition for thin film printing, and method for forming thin film conductive pattern
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WO2018169672A1 (en) * 2017-03-13 2018-09-20 Eastman Kodak Company Silver-containing compositions containing cellulosic polymers and uses
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